Article No : a20_459

Plastics, Additives
RAINER WOLF, Sandoz Huningue S.A., Huningue, France
BANSI LAL KAUL, Sandoz Huningue S.A., Huningue, France

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 620 5.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 645

2. Antioxidants. . . . . . . . . . . . . . . . . . . . . . . . 620 5.6. Economic Aspects . . . . . . . . . . . . . ..... . 646
2.1. Purpose and Requirements . . . . . . . . . . . . 620 6. Flame Retardants . . . . . . . . . . . . . ..... . 646
2.2. Chemical Classes . . . . . . . . . . . . . . . . . . . . 621 6.1. Purpose and Requirements . . . . . . ..... . 646
2.3. Mechanism of Action . . . . . . . . . . . . . . . . . 623 6.2. Chemical Classes . . . . . . . . . . . . . . ..... . 647
2.4. Test Methods . . . . . . . . . . . . . . . . . . . . . . . 624 6.3. Mechanism of Action . . . . . . . . . . . ..... . 651
2.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 624 6.4. Test Methods and Standards . . . . . ..... . 654
2.6. Legal Aspects. . . . . . . . . . . . . . . . . . . . . . . 626 6.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 654
2.7. Economic Aspects . . . . . . . . . . . . . . . . . . . 626 6.6. Toxicology . . . . . . . . . . . . . . . . . . . ..... . 657
3. Light Stabilizers. . . . . . . . . . . . . . . . . . . . . 627 6.7. Economic Aspects . . . . . . . . . . . . . ..... . 657
3.1. Purpose and Requirements . . . . . . . . . . . . 627 7. Fillers and Coupling Agents . . . . . ..... . 657
3.2. Chemical Classes . . . . . . . . . . . . . . . . . . . . 628 7.1. Purpose and Requirements . . . . . . ..... . 657
3.3. Mechanism of Action . . . . . . . . . . . . . . . . . 628 7.2. Forms and Chemical Structures . . ..... . 658
3.4. Test Methods . . . . . . . . . . . . . . . . . . . . . . . 637 7.3. Mechanism of Action . . . . . . . . . . . ..... . 658
3.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 637 7.4. Test Methods . . . . . . . . . . . . . . . . . ..... . 659
3.6. Economic Aspects . . . . . . . . . . . . . . . . . . . 638 7.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . ..... . 659
4. Heat Stabilizers for Poly(Vinyl Chloride) . 638 7.6. Economic Aspects . . . . . . . . . . . . . ..... . 661
4.1. Purpose and Requirements . . . . . . . . . . . . 638 8. Dyes and Pigments . . . . . . . . . . . . ..... . 661
4.2. Chemical Classes . . . . . . . . . . . . . . . . . . . . 639 8.1. Requirements . . . . . . . . . . . . . . . . ..... . 661
4.2.1. Metal-Containing Stabilizers . . . . . . . . . . . . 639 8.2. Pigments . . . . . . . . . . . . . . . . . . . . ..... . 662
4.2.2. Metal-Free Stabilizers . . . . . . . . . . . . . . . . . 640 8.2.1. Inorganic Pigments . . . . . . . . . . . . . ..... . 662
4.3. Mechanism of Action . . . . . . . . . . . . . . . . . 640 8.2.2. Organic Pigments . . . . . . . . . . . . . . ..... . 663
4.4. Test Methods . . . . . . . . . . . . . . . . . . . . . . . 641 8.2.3. Dyes . . . . . . . . . . . . . . . . . . . . . . . ..... . 663
4.5. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641 9. Miscellaneous Additives. . . . . . . . . ..... . 664
4.6. Economic Aspects . . . . . . . . . . . . . . . . . . . 642 9.1. Nucleating Agents . . . . . . . . . . . . . ..... . 664
5. Lubricants, Slip, Antiblocking, 9.2. Antistatic Agents . . . . . . . . . . . . . . ..... . 665
and Mold-Release Agents. . . . . . . . . . . . . . 643 9.3. Impact Modifiers . . . . . . . . . . . . . . ..... . 666
5.1. Purpose and Requirements . . . . . . . . . . . . 643 9.4. Chemical Blowing Agents . . . . . . . ..... . 667
5.2. Chemical Classes . . . . . . . . . . . . . . . . . . . . 643 9.5. Optical Brighteners . . . . . . . . . . . . ..... . 669
5.3. Mechanism of Action . . . . . . . . . . . . . . . . . 644 References . . . . . . . . . . . . . . . . . . . ..... . 669
5.4. Test Methods . . . . . . . . . . . . . . . . . . . . . . . 644

Abbreviations: LDPE: low-density polyethylene

LLDPE: linear low-density polyethylene
ABS: acrylonitrile – butadiene – styrene
PETP: poly(ethylene terephthalate)
polymer
PVC: poly(vinyl chloride)
HIPS: high-impact polystyrene
SAN: styrene – acrylonitrile copolymer
PBT: poly(butylene terephthalate)
HDPE: high-density polyethylene

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a20_459
620 Plastics, Additives Vol. 27

1. Introduction
As plastics find new applications, they face
increasingly stringent requirements regarding
their service life, durability, and many other
properties. A variety of approaches are taken to
meet these requirements. One approach is to
modify the chemistry of the macromolecules
from which plastics are made (e.g., by using new
monomers or copolymerization). Current devel-
opments in the area of polymer blends also offer
a great deal of scope for innovation. Another
important way of improving the properties of
plastics is to employ additives. These agents have
made a decisive contribution to the widespread
use of plastics and promise to be useful tools for
solving future problems.
Plastics additives can be classified into three Figure 1. World consumption of plastics additives excluding
main groups: fillers and pigments in 1990 (100 % ¼ 1.7
106 t) a) Lubri-
cants and related compounds; b) Antioxidants; c) Light
stabilizers; d) Miscellaneous additives; e) Flame retardants;
1. Additives that stabilize plastics against deg- f) Plasticizers; g) Poly(vinyl chloride) heat stabilizers;
radation and aging during processing or in h) Impact modifiers
use. Degradation usually involves chain
cleavage of the macromolecules and can pro- Although additives can be added to the mono-
ceed through the addition of energy (e.g., mer prior to polymerization, they are usually
shear forces, heat, UV light) or chemical introduced immediately after polymerization,
attack (e.g., oxidation, hydrolysis). These blended, and extruded to form granular (pellet-
additives are called antioxidants, light stabi- ized) products and compounds. Many additives
lizers, or heat stabilizers. are not introduced until the granules are pro-
2. Additives that facilitate or control processing cessed into moldings, films, or fibers.
(e.g., lubricants, mold-release agents, or Additives with monomer functions can be
blowing agents). incorporated chemically into the plastic if they
3. Additives that impart new, desirable qualities are introduced before polymerization. In the case
to plastics, such as resistance to burning, trans- of agents added before processing, the use of
parency or color, improved mechanical or ‘‘masterbatches’’ (i.e., granular products contain-
electrical properties, dimensional stability, and ing the concentrated additive in a polymer vehi-
degradability. Such additives include flame cle) is often advisable.
retardants, fillers, dyes, pigments, antistatic Plastics generally contain many additives.
agents, nucleating agents, optical brighteners, Preblended additive systems and combination
impact modifiers, and plasticizers. Plasticizers masterbatches are commercially available; they
are discussed elsewhere, ! Plasticizers. contain optimal proportions of additives that are
mutually compatible or have a synergistic action.
Surveys of additive groups are given in [1],
[2]. New developments are published monthly
2. Antioxidants
in [3]. The total amount of additives (excluding
fillers and pigments) used worldwide by the
See also ! Antioxidants.
plastics industry in 1990 is estimated at ca.
1.7
106 t (Fig. 1).
The concentration of additives varies greatly, 2.1. Purpose and Requirements
ranging from a few parts per million for some
stabilizers to more than 50 % for certain flame Antioxidants prevent or retard the autoxidation
retardants or fillers. of polymers and minimize associated damage
Vol. 27 Plastics, Additives 621

(e.g., discoloration, reduction in gloss, cracking, or phenol and thioethers). Antagonistic effects
embrittlement); i.e., they stabilize the physical are also observed, however (e.g., between
properties of plastics. Oxidation reactions gener- thioethers and HALS) [5].
ally proceed via different mechanisms that The stabilizer system often includes other
depend on the structure of the polymer. They components that complex or neutralize degrada-
are often catalyzed by catalyst residues and tion-promoting catalysts or acid traces. These
contaminants. They are also accelerated by the may be metal deactivators (oxamides, hydra-
addition of thermal or mechanical energy during zones, and hydrazides) or acid scavengers [cal-
plastics production and processing. cium or magnesium stearate, hydrotalcite (basic
Three forms of stabilization are used: presta- Mg/Al carbonate), and epoxy compounds].
bilization, stabilization during processing, and
long-term stabilization. Sterically Hindered Phenols. Industrial
Most antioxidants are themselves oxidized products are mostly derived from 2,6-di-tert-
and consumed in performing their function, so butylphenol (1; n ¼ 1, R ¼ H); or, less often,
that the oxidation behavior of the additive in a from2-tert-butyl-6-methylphenol, 2-tert-butyl-
given polymer is crucial for its effectiveness [4]. 5-methylphenol, or other hindered phenols.
A number of other requirements apply to Tabulations are given in the literature [1], [6].
antioxidants:

1. They must be thermally stable and nonvolatile

at processing temperatures
2. They must be soluble in polymers and no
chalking should occur at service temperatures
3. They must not have an intrinsic color, and
their oxidation products must have minimal The simplest representative and oldest prod-
color uct of this class is 2,6-di-tert-butyl-4-methylphe-
4. Any acidic hydrolysis products must not cor- nol [128-37-0] (butylated hydroxytoluene, BHT)
rode machinery with n ¼ 1 and R ¼ CH3. Variation of n from
5. They must resist extraction 1 to 4 and of R results in a range of hindered
6. They must be odorless and tasteless phenols with high molecular mass and thus low
7. They must not create toxicity problems (many volatility, good solubility in certain polymers,
must be approved as indirect food additives) and only slightly colored oxidation products.
Products 2–4 are commonly used.
2.2. Chemical Classes

Antioxidants are divided into two classes on the

basis of their mode of action (see Section 2.3):

1. Primary antioxidants : sterically hindered

phenols, secondary aromatic amines, and ste-
rically hindered amines (HALS)
2. Secondary antioxidants: phosphites, phos-
phonites, thioethers (sulfides), and metal salts

Primary antioxidants can be used by them-

selves for prestabilization and long-term
stabilization. Secondary antioxidants are used
in combination with primary antioxidants, espe-
cially for stabilization during processing and for
long-term stabilization under severe thermal
conditions. Synergistic effects often occur in
such systems (e.g., phenol and phosph(on)ites
622 Plastics, Additives Vol. 27

The natural compound a-tocopherol [59-02-9] The cyclic phosphites 10, 11 [9], and 12 [10]
or vitamin E (5) is also used as an antioxidant are also available:
[7], [8].

Secondary Aromatic Amines and Dihydro-

quinolines. Industrial products are derived
chiefly from diphenylamine or p-phenylenedia-
mine. A widely used representative of this class is
4-isopropylaminodiphenylamine [101-72-4] (6):

2,2,4-Trimethyl-1,2-dihydroquinoline [147-
47-7] (7) should also be mentioned:

Compound 13 is an industrially used phos-

phonite antioxidant [11]:

Sterically Hindered Amines (HALS). The

abbreviation HALS stands for ‘‘hindered amine
light stabilizers.’’ They are described in more
detail in Chapter 3 and are based on the 2,2,6,6-
tetramethylpiperidine structure.

Phosphites and Phosphonites. The sim- The substituents influence not only the vola-
plest industrial phosphite antioxidants are tris tility and the solubility in polymers, but also the
(nonylphenyl) phosphite [26523-78-4] (TNPP) stability of the product to hydrolysis.
(8) and tris(2,4-di-tert-butyl) phosphite [31570-
04-4] (9). Organosulfur Compounds. Organosulfur
antioxidants in practical use are the dilauryl
[123-28-4] (14, n ¼ 12), dimyristyl [16545-
54-3] (14,n ¼ 14), and distearyl [693-36-7]
(14, n ¼ 18) esters of thiodipropionic acid (14)
which are abbreviated as DLTDP, DMTDP, and
DSTDP, respectively.
Vol. 27 Plastics, Additives 623

Disulfides such as dioctadecanyl disulfide or participate in reactions catalyzed by trace

. .
[2500-88-1] or higher molecular mass products metals to form oxy (RO , HO ) or peroxy radicals
.
such as 15 are used less often. (ROO ), which cleave additional bonds in the
polymer and generate new radical sites in the
chain or break the polymer chain to give carbonyl
groups:

Metal Compounds. Zinc and nickel dithio-

carbamates or mercaptobenzimidazoles are
sometimes used.
The extent of thermooxidative degradation
Metal Deactivators. The oxamides or hy- in many polymers can be estimated via the
drazine derivatives used as metal deactivators concentration of peroxy radicals, hydroperoxide
often have hindered phenol functions in the groups, and carbonyl groups. Macroradicals can
molecule as well, so that they also have a primary also react with C¼C bonds in the polymer,
antioxidant action [1]. A typical structure is: especially with vinyl groups [12], or can recom-
bine and result in undesirable cross-linking (gel
formation).
Antioxidants act by trapping free radicals
formed in the polymer (primary antioxidants),
reduce hydroperoxides to hydroxyl groups (sec-
ondary antioxidants), or form complexes with
trace metals that would otherwise catalyze
hydroperoxide decomposition (metal deactiva-
2.3. Mechanism of Action tors). Antioxidant mechanisms are described in
[13–18]; see also ! Antioxidants, Section
Thermooxidative degradation is an autocatalytic, 3.2.! Antioxidants.
free-radical chain reaction that involves initia-
tion, propagation, branching, and termination Hindered Phenols. Hindered phenols are
.
stages. Primary radical sites R are initially radical-trapping antioxidants for oxy and espe-
formed by the abstraction of labile hydrogen cially peroxy radicals:
atoms (e.g., tertiary or allylic hydrogens or
those in the a-position to ether oxygen or amide
nitrogen atoms). In the presence of oxygen, the
primary radicals are oxidized to peroxy radicals
.
ROO . The peroxy radicals then take part in
intermolecular (Eq. 1) and intramolecular
(Eq. 2) chain propagation reactions to form new
The phenoxy radicals with their bulky sub-
radical sites and hydroperoxides:
stituents are stabilized by steric hindrance and
cannot attack the polymer. These radicals are
transformed to quinonoid structures that can
recombine with other peroxy radicals:

The chain propagation reactions are rate

determining for thermooxidative degradation.
Tertiary hydrogen atoms are about three times
more reactive than secondary hydrogens. The The formation of yellow quinonoids is a
hydroperoxides undergo thermal decomposition drawback of this class. The intensity of the color
624 Plastics, Additives Vol. 27

depends on the structure of R1 ; it is particularly manganese (from fillers), and titanium (from
high in the case of BHT due to the formation of polymerization catalysts).
stilbenequinones. For the effects of metals and metal deactiva-
tors, see [23].
Secondary Aromatic Amines also act by
trapping peroxy radicals. Since the products
derived from secondary aromatic amines are 2.4. Test Methods
generally dark in color, their use is restricted to
colored elastomers. Their stabilizing action The two most important test methods for anti-
against ozone degradation should be noted. oxidants are the multiple extrusion test and the
oven test (DIN 53 383, ASTM D 1870–68).
HALS are used primarily as light stabili- The multiple extrusion test examines degra-
zers. They can trap both carbon radicals and dation in the polymer melt (i.e., stabilization
peroxy radicals at ambient temperatures. The during processing). The antioxidant is blended
active species is a hindered nitroxyl radical, with the polymer, and the resulting granules are
which is regenerated (see Chap. 3). HALS are regranulated up to ten times in succession in an
effective long-term stabilizers [19], [20]; non- extruder under defined temperature conditions.
volatile, high molecular mass derivatives are The yellowness index (ASTM D 1925–70) and
especially useful [21]. the melt viscosity (melt flow index, MFI, ASTM
D 1238–70) or solution viscosity are measured.
Phosphites and Phosphonites. The second- The melt viscosity can also be determined on-line
ary phosphite and phosphonite antioxidants in an extruder equipped with a bypass [24].
reduce hydroperoxides and are themselves oxi- In the oven test, polymer degradation is stud-
dized to phosphates and phosphonates: ied in the solid phase (i.e., long-term stabilization
is determined). Test plates of the polymer are
PIII þROOH!PV þROH placed on rotating trays in special furnaces with
air recirculation. Their appearance (browning,
Peroxy radicals are analogously reduced to oxy
reduction in gloss and transparency), mechanical
radicals. Phosphites and phosphonites may also
properties (brittleness, tensile strength, impact
complex and thus deactivate trace metals (e.g.,
strength), and analytical data (carbonyl bands in
polymerization catalyst residues). Their oxida-
the IR) are evaluated after various times. To
tion products are colorless, so they are particu-
shorten the test period, the oven test is often run
larly successful as color stabilizers. Their action
at 100 – 150  C, but correlation of the results
is especially useful in the processing of polymer
with room temperature is problematic especially
melts, where they also protect phenolic antiox-
in the case of metal deactivators.
idants against premature oxidation.
Other test methods include
Organosulfur Compounds decompose
1. Thermogravimetric analysis, especially for
hydroperoxides. Sulfides, for example, are con-
plastics such as polyoxymethylene that tend
verted to sulfoxides, sulfenic acids, and sulfur
to undergo thermal depolymerization
dioxide, which in turn can reduce further hydro-
2. Torque measurements on polymer melts in
peroxides. Sulfur-containing stabilizers can
the Brabender, especially for plastics that tend
also regenerate phenolic antioxidants from their
to cross-link (e.g., polyethylene)
quinonoid structures. Their action is most pro-
3. Transparency measurements on extruded films
nounced at higher temperatures in solid plastics.
4. Determination of the induction period in an
The odor of the reaction products can be a
oxygen absorption test at elevated tempera-
drawback.
ture (OIT test)
Metal Deactivators act by chelating metal
ions [22], particularly metals that have a number 2.5. Uses
of oxidation states and catalyze hydroperoxide
decomposition even at low temperatures. These Polyolefins. The optimal antioxidants for
metals include copper (from cablewires), iron, polyolefins depend on the type of resin,
Vol. 27 Plastics, Additives 625

production process (catalyst; solution, suspen- low-density polyethylene (LLDPE), respective-

sion, or bulk polymerization), comonomer, filler, ly. Whereas polypropylene exhibits an increase
application (moldings, films, fibers), and other in melt flow index (degradation by chain cleav-
factors. Modern bulk polymerization processes, age), LLDPE shows a decline (degradation dom-
in which purification steps are omitted or poly- inated by cross-linking).
mers are produced directly as spherical granules, The selection of antioxidants also depends on
have led to reformulation of stabilization the solubility in the polymer, which is especially
systems. critical for LLDPE. If the polymerization process
The primary antioxidant BHT, with its high already yields a granular product in the reactor,
volatility and yellowing tendency, is losing antioxidants can be applied to the reactor gran-
ground to higher molecular mass hindered ules by spraying on the surface. Low-melting
phenols (e.g., 2–4). For prestabilization up to products such as 13 are especially suitable for this
250 ppm of 3 is usually added at the polymeri- purpose.
zation stage; ca. 500 – 1000 ppm of a phenolic Thioethers are preferentially used as syner-
antioxidant is subsequently added for stabiliza- gists when severe thermal requirements apply to
tion during processing and service. Higher long-term stabilization. They are employed at
concentrations are seldom used because of the concentrations of ca. 1000 – 3000 ppm.
risk of yellowing. Metal deactivators are used at the 500 –
The main secondary antioxidants used during 5000 ppm level (higher concentrations in talc-
processing are the phosphites 8–10 and the phos- filled polypropylene).
phonite 13, whereby especially 13 not only sta- Other formulation guidelines are given in [1].
bilizes the melt viscosity but also offers much
better color stabilization than phosphites such as Styrene Polymers. Phenolic antioxidants
8 and 9. The phosph(on)ites are used at concen- (up to 2000 ppm) are added to high-impact
trations of 500 – 2000 ppm. polystyrene modified with polybutadiene. They
Figures 2 and 3 illustrate the stabilization are usually introduced before polymerization.
obtained with phosphites and phosphonites dur- Phosphites and phosphonites are sometimes em-
ing the processing of polypropylene and linear ployed as color stabilizers.

Figure 2. Stabilization of polypropylene in a multiple extrusion test with 0.1 % phenolic antioxidant (2) and 0.1 % calcium
stearate as basic stabilization and 0.1 % phosph(on)ite process stabilizer a) Phosphite (9); b) Phosphite (10a); c) Phosphite (12);
d) Phosphonite (13); e) Phosphite (11); f) No process stabilizer
626 Plastics, Additives Vol. 27

Figure 3. Stabilization of linear low-density polyethylene in a multiple extrusion test with 0.1 % phenolic antioxidant (3) and
0.1 % calcium stearate as basic stabilization and 0.15 % phosph(on)ite process stabilizer a) Phosphite (9); b) Phosphite (10a);
c) Phosphite (10b); d) Phosphonite (13); e) No process stabilizer

In acrylonitrile – butadiene – styrene copo- Germany). Unified approvals are expected to

lymers (ABS), the antioxidants are usually intro- apply throughout the EC as of 1993. Approval
duced into the polybutadiene latex phase by is based on toxicity and extraction tests (extrac-
emulsification before it is blended with polysty- tion of antioxidants from plastics by food simu-
rene – polyacrylonitrile. Along with 1000 – lants). Most well-established antioxidants have
2000 ppm of phenolic antioxidants, larger received broad approval for food use.
amounts of phosphite 8 or DLTDP are used.

Other Plastics. [1]. Antioxidants play a less 2.7. Economic Aspects

important role in plastics other than polyolefins
and the styrene polymers described above. Table 1 presents 1990 market volumes of
Secondary aromatic amines, BHT, TNPP, as well antioxidants. Polyolefins, ABS, and polysty-
as high molecular mass phenols are used in rene account for ca. 80 – 90 % of the antioxi-
elastomers and polyurethanes. dant market. Prices of antioxidants are given
Although engineering thermoplastics (e.g., in [25].
polycarbonates, polyesters, polyamides) are less Antioxidants are often marketed in the form
sensitive to thermooxidative degradation, hin- of powder blends. The most important producers
dered phenols and phosph(on)ites are used for and trade names are listed in Table 2.
color stabilization or long-term stabilization.

Table 1. Estimated market volume of antioxidants in 1990 (103 t)

2.6. Legal Aspects
Region Phenols Thioethers Phosph(on)ites Other Total
Because plastics are widely used in food pack- United States 14 3 6 2 25
aging and agriculture, antioxidants must be ap- Western Europe 15 3 7 3 28
proved as indirect food additives by national Japan 8 2 3 2 15
agencies such as the FDA (USA) and the Other 10 2 3 2 17
Total 47 10 19 9 85
Bundesgesundheitsamt (Federal Health Office,
Vol. 27 Plastics, Additives 627

Table 2. Manufacturers and trade names of antioxidants

Manufacturer Trade names Phenols Phosph(on)ites Thioethers Aromatic Metal Blends

amines deactivators

Adeka Argus Mark X X X X X

Akzo Chemie Perkanox X
American Cyanamid Cyanox X X X
BASF Sicostab X X
Bayer Vulkanox X X
B. F. Goodrich Chem. Goodrite X X
Chem. Werke Lowi Lowinox X X
Ciba-Geigy Irganox, Irgafos X X X X X
Daiichi Kogyo Seiyaku Lasumit X
Dover Chemicals Doverphos X
Eastman Chemicals Tenox X X
Enichem Synthesis Anox, Alkanox X X X
Ethyl Corporation Ethanox X X
Ferro Corporation Oxi-chek X
General Electric Ultranox, Weston X X X X
W. R. Grace X
Hitachi Cunox X
Hoechst Hostanox X X X X
ICI Nonox, Topanol X X X
Jokoku Chemicals X
Mitsubishi Petrochem. Seenox X X
Monsanto Santonox, Santowhite X X
Flectol
Morton Thiokol Carstab X
Olin Chemicals Wytox X X
Pennwalt Anoxyn X
PMC Specialities Group Prodox X
Raschig Ralox X
Rhône-Poulenc Rhodianox, Garbafix X X
R. T. Vanderbilt AgeRite, Vanox X X X X
Sandoz Chemicals Sandostab X
Schenectady Chemicals Isonox X
Shell Ionol, Ionox X
Shipro Kasei Seenox X X
Sumitomo Sumilizer X X X
Ube Industries X
Uniroyal Naugard, Aranox X X X X X
Witco Mark X X X X
Yoshitomo X

3. Light Stabilizers disintegrate. Light stabilizers are used to maxi-

mize protection against photodegradation.
3.1. Purpose and Requirements Ultraviolet radiation is subdivided into UV-A
(l ¼ 320 – 400 nm), UV-B (l ¼ 280 –
Synthetic and natural polymers vary in their 320 nm), and UV-C (l <280 nm). Only UV-A
sensitivity to environmental influences. Ultravi- and UV-B reach the Earth’s surface in sunlight,
olet radiation in sunlight plays a critical role and UV-B is largely responsible for the degrada-
because it has sufficient energy to break chemical tion of plastics.
bonds. The cleavage sites react with atmospheric The difference in damage (yellowing) caused
oxygen and accelerate degradation (free-radical by UV-A and UV-B in poly(vinyl chloride)
chain reactions; see Section 2.3). Many plastics (PVC) is shown in Figure 4. Plastics are generally
therefore suffer yellowing, surface cracking, em- fairly stable in the long-wavelength UV-A
brittlement, reduction of gloss, or chalking after (350 – 400 nm). Most plastics are sensitive to
a short time in outdoor service, and ultimately wavelengths of 290 – 320 nm.
628 Plastics, Additives Vol. 27

3. Radical scavengers: hindered amines (HALS)

and 4-hydroxybenzoates (HB)

Table 3 lists some of the most important light

stabilizers now in use, along with their trade
names and producers.
Stabilization can also be achieved by incor-
poration of carbon black, titanium dioxide, or
zinc oxide. The effect of colored pigments varies:
phthalocyanine blue pigments have a stabilizing
action; organic red and yellow pigments sensitize
photodegradation.

Figure 4. Damage in PVC as a function of the wavelength of

UV light (300-h radiation) 3.3. Mechanism of Action

Two methods are used to protect plastics Photodegradation of Polymers. Photode-

against photodegradation: (1) incorporation of gradation is initiated when radiation is absorbed
light stabilizers in the bulk plastic, and (2) coat- by chromophores in the polymer structure itself
ing with a light-stable or light-stabilized material (e.g., C¼C, C¼O) or by impurities or defects.
that is largely opaque to the dangerous UV range. Energy can be dissipated from excited states by
Light stabilizers must have high light emission of radiation (fluorescence from short-
absorption; must resist extraction with water, lived singlet states or phosphorescence from
hydrolysis, and thermal volatilization; and must long-lived triplet states), release of heat, or ener-
themselves be stable toward UV radiation. Ide- gy transfer to nearby chromophores. If none of
ally, a light stabilizer should not be consumed these mechanisms is available, photodegradation
while carrying out its function; it should operate takes place with bond cleavage and formation
in a closed cycle so that it still exists in active of radicals. These radical sites react with
form even after a long period of weathering oxygen and initiate autoxidative chain reactions.
or use. Excited molecular segments can also transfer
Other requirements include solubility in the energy to oxygen, converting it to higher-energy
polymer, stability under processing conditions, singlet oxygen, which accelerates oxidative
compatibility with other additives, and colorless- degradation.
ness. In certain applications, light stabilizers Oxidation to carbonyl groups in the macro-
must be approved as indirect food additives. molecules results in chain cleavage via the Nor-
The service life of a plastic is more than rish reactions:
doubled by light stabilizers. Modern systems
extend service life by a factor of 10 – 20 in many
plastics, thus permitting their outdoor use.

3.2. Chemical Classes

Light stabilizers are classified in three groups

according to their mode of action: Many plastics with aromatic residues (e.g.,
polycarbonates, polyesters, polyamides) tend to
1. UV absorbers: 2-hydroxybenzophenones participate in ‘‘photo-Fries reactions’’, whose
(BP-UVA), 2-hydroxyphenylbenzotriazoles products may be colored or may be precursors
(BT-UVA), oxalanilides (OA-UVA), 2-hy- of colored products:
droxyphenyltriazines (TA-UVA), cinnamates
(CA-UVA), salicylates (SA-UVA), and for-
mamidines (FA-UVA)
2. Energy quenchers: nickel complexes (NIC)
Vol. 27 Plastics, Additives 629

Table 3. Light stabilizers

(Continued )
630 Plastics, Additives Vol. 27

Table 3 (Continued )
Vol. 27 Plastics, Additives 631

Table 3 (Continued )

(Continued )
632 Plastics, Additives Vol. 27

Table 3 (Continued )
Vol. 27 Plastics, Additives 633

Table 3 (Continued )

(Continued )
634 Plastics, Additives Vol. 27

Table 3 (Continued )
Vol. 27 Plastics, Additives 635

Table 3 (Continued )
636 Plastics, Additives Vol. 27

In semicrystalline plastics, UV radiation is

scattered by the crystallites and increases the
quantum efficiency of polymer degradation.
Photodegradation occurs mainly in the amor-
phous, oxygen-permeable regions.

Ultraviolet Absorbers. The UV absorbers

listed in Table 3 have intense absorption bands
in the UV-B and some of them in the UV-A as
well. They therefore filter out harmful radiation
before it reaches the chromophores in the
plastic.
The UV absorbers must dissipate the absorbed
energy quickly as heat and not as radiation.
Mechanisms proposed for this action include
proton transitions in the excited singlet state
[26–28]. Other quenching mechanisms have also Figure 5. Stabilization mechanism of HALS
been postulated [29].
The position and intensity of absorption can
be modified by substituents on the aromatic rings.
For example, alkoxy substituents in the 4- and [30]. The hindered amines (HALS) are much
40 -positions of 2-hydroxybenzophenones bring more important, however; they all have a
about bathochromic shifts in the absorption 2,2,6,6-tetramethylpiperidine ring [31]. The
maxima, as do alkyl substituents in the phenyl cyclic mode of action of HALS is shown in
ring of 2-hydroxyphenylbenzotriazoles. The Figure 5 [32–43]. The stabilizing action is due
steepness of the UV absorption curve on the not to the HALS compound itself (N – R1) but to
.
long-wavelength side is important with respect the nitroxyl radical (N – O ) formed by photo-
to intrinsic color—even slight residual absorp- oxidation during weathering. The nitroxyl
tion around 400 nm causes yellow coloration. radical reacts with the polymer radicals formed
The UV absorbers hinder the photolysis of by photolysis to give ethers (N – O – R), which
polymers by competing for UV absorption. They then react with peroxy radicals to regenerate the
are thus particularly effective when degradation nitroxyl radical. Other mechanisms are based on
is due primarily to photolysis and not to oxida- the trapping of acyl peroxide radicals [44] or the
tion. Since the intensity of radiation depends on decomposition of hydroperoxides [45].
the thickness of the absorbing layer (Lambert – The action of HALS depends on their concen-
Beer law), these substances are more effective tration and not on layer thickness. They are
within the plastic than at its surface. They are therefore equally as effective at the surfaces of
therefore only marginally effective in thin films plastics in films, fibers, coatings, and thick layers.
and fibers. They are, however, sensitive to certain chemi-
cals, such as organic thioether costabilizers [5],
Energy Quenchers. Light stabilizers based halogen flame retardants [46], kaolin fillers,
on nickel complexes, like some UV absorbers, pesticides [47], and acids. Synergistic effects
are energy quenchers. They absorb energy from between HALS and UV absorbers are widely
excited polymer regions or from singlet oxygen, used in industry, and synergies have also been
and dissipate it as heat. The action of quenchers observed with nickel quenchers [48]. A combi-
depends on concentration, not on layer nation of low molecular mass HALS (which
thickness. migrate to the surface) and high molecular mass
compounds (which are more strongly anchored
Radical Scavengers. Sterically hindered in the bulk polymer) is also recommended [21].
4-hydroxybenzoates and amines act chiefly as Recent developments include 2,2,6,6-tetra-
radical scavengers. 4-Hydroxybenzoates can be methylpiperazinones [49] and HALS that are
regarded as photostable phenolic antioxidants chemically bound to polyolefins [50].
Vol. 27 Plastics, Additives 637

3.4. Test Methods Table 4. Devices for accelerated weathering tests

Producer Device Light source

Light stabilizers are incorporated into polymers;
processed into specimens in plate, film, fiber, or W.C. Heraeus GmbH, Xenontest xenon lamps
Hanau, Germany
coating form; and then exposed to radiation in Suntest
the presence or absence of moisture to determine Atlas Electric Devices Weather-Ometer xenon lamps
their weather resistance and lightfastness, Company, Chicago,
respectively. USA
Fade-Ometer carbon-arc lamps
Weathering may be natural or artificial (i.e., Sunchex UV fluorescent
accelerated). Changes in color (DIN 53 236), tubes
yellowness index (ASTM D 1925–70), gloss UV-CON
(DIN 67 530), cracking (ISO 4628 Part 4), tensile Q-Panel Company, Q-U-V UV fluorescent
Cleveland, USA tubes
strength, elongation at break (ASTM D 638, ISO Weiss Technik AG, Global-UV-Testger€at special UV lamps
IR 527), or impact resistance (ASTM D 256, Reiskirchen, Germany
ISO R 179) are used to assess lightfastness and Bauart BAM
weather resistance. The intensity of the IR car- Dainippon Plastics, Eye Super UV Tester special UV lamps
Tokyo, Japan
bonyl bands is also very often used as a criterion
of photodegradation. See also ! Paints and
Coatings, 1. Introduction; ! Plastics, Properties um seating, window frames, floor coverings)
and Testing, Section 2.7.3.. films for protective coverage and agriculture;
light fixtures and illuminated signs; automotive
Open-Air Weathering Tests are performed parts such as bumpers and body paints; and sports
on a commercial basis in all climatic zones. equipment and clothing. Light stabilizers extend
Important sites are located in Central Europe the service lives of these articles by years.
(temperate climate), southern Florida (subtropi- The approximate breakdown of light stabi-
cal), Arizona (desert climate), Okinawa, Thai- lizer uses according to type of plastic is as
land, Australia, South Africa, Israel, and follows:
Singapore.
In accelerated sunlight tests, Fresnel reflec- Polyolefins (polyethylene, polypropylene) 55 %
Acrylic and polyurethane coatings 20 %
tors are used to focus sunlight on the specimens PVC 10 %
(ASTM E 838–81). Examples of such tests in- ABS and polystyrene 5%
clude the Equatorial Mount with Mirrors for Unsaturated polyester resins 4%
Acceleration (EMMA) test and the Equatorial Miscellaneous substrates 6%
Mount with Mirrors for Acceleration plus Water
Spray (EMMAQUA) test, which are performed The stabilizers are generally used in concen-
in Arizona. trations of 0.05 – 0.5 %, reaching 3 % in espe-
In artificial weathering the specimens are cially critical applications. Recommended
subjected to precisely defined climatic condi- formulations can be found in [1].
tions (temperature, irradiation, rainfall) in spe-
cially designed apparatus. Xenon arcs, carbon Polypropylene. is particularly sensitive to
arcs, and fluorescent lamps are used as illumina- photodegradation. The photostabilization of
tion sources (see Table 4); filtered xenon light polypropylene is reviewed in [53]. Thick mold-
best simulates global irradiation [51], [52]. ings are stabilized with 0.2 – 0.6 % of UV ab-
Standards for artificial weathering tests sorbers (e.g., BP-UVA 1, BT-UVA 2) and/or
include DIN 53 384, DIN 53 231, and ANSI/ radical scavengers (e.g., HB-1 and 2, HALS
ASTM G 53–57. 1 – 8). HALS (chiefly of high molecular mass,
such as HALS 1, 4, or 5) are employed to stabilize
films and fibers.
3.5. Uses
Polyethylene. Although polyethylene is
Light stabilizers are employed mainly in plastics more stable to light than polypropylene, it re-
for outdoor service (e.g., garden furniture, stadi- quires good stabilization for outdoor service.
638 Plastics, Additives Vol. 27

The selection of light stabilizers is especially Table 5. Estimated market volume of light stabilizers in 1990 (103 t)
critical because of the danger of surface chalking Region BP-UVA BT-UVA HALS Others Total
due to migration of incompatible additives.
Low-density and linear low-density polyethyl- United States 1.1 1.7 2.4 0.6 5.8
Western Europe 1.0 1.4 2.2 0.6 5.2
ene (LDPE and LLDPE) films contain up to Japan 0.4 1.3 1.3 0.3 3.3
0.4 % of a nickel quencher and UV absorber Other 0.4 0.9 1.1 0.3 2.7
combination (e.g., NIC-1 and BP-UVA 1) or of Total 2.9 5.3 7.0 1.8 17.0
a polymeric HALS (e.g., HALS 1, 4, or 7). In
filled grades, higher concentrations (ca. 1.5 %)
can also produce more than a tenfold increase in
service life in open-air weathering. In high- 3.6. Economic Aspects
density polyethylene (HDPE) the best results are
obtained with HALS (e.g., HALS 2, 4, or 7); Market volumes for light stabilizers are given in
0.1 % is often sufficient. Table 5. The most important producers and trade
names are listed in Table 3.
Roughly 50 % of the light stabilizers are sold
Styrene Polymers. The UV absorbers and
to plastics processors in the form of master-
UV absorbers – HALS combinations (e.g.,
batches (concentrates containing  20 % light
BT-UVA 1 with HALS 2) are recommended for
stabilizers in appropriate polymer vehicles).
polystyrene, ABS, and styrene – acrylonitrile
Combination masterbatches supplemented with
copolymers (SAN) at a total concentration of
pigments or flame retardants are being
ca. 1 % [54].
developed.

Poly(Vinyl Chloride). The lightfastness of

PVC depends heavily on its heat stabilization or 4. Heat Stabilizers for
fillers. Barium and cadmium stabilizers, tin car- Poly(Vinyl Chloride)
boxylates, and titanium dioxide substantially
improve lightfastness. Tin mercaptides are un- 4.1. Purpose and Requirements
suitable for outdoor service or necessitate high
levels of titanium dioxide. HALS are not very Poly(vinyl chloride) (PVC) is thermally unsta-
effective. For transparent PVC in particular, the ble. Heating results in elimination of HCl, the
use of 0.1 – 0.3 % UV absorbers (e.g., BP-UVA formation of polyene sequences, and rapid dis-
1 or 2, BT-UVA 1 or 5, OA-UVA 1) is coloration. This autocatalytic reaction begins at
recommended. ca. 100  C; at 180  C a marked brown color
occurs after a few minutes. Special heat stabi-
Miscellaneous Plastics. Polyurethanes, es- lizers are therefore required for the processing
pecially those derived from aromatic isocyanates and use of this high-tonnage plastic. These ad-
and polyether polyols, tend to yellow and show ditives are rated according to several criteria
a deterioration of mechanical properties when besides their efficiency as heat stabilizers:
exposed to light. Ternary combinations of
HALS, UV absorbers, and phenolic antioxidants 1. Versatility (use with mass, suspension, and
have a good stabilizing action, especially in emulsion PVC)
foamed plastics [55]. 2. Effect on melt rheology of PVC
The UV absorbers (e.g., benzotriazoles such 3. Lubricant action
as BT-UVA 1 and 2) and HALS are used to 4. Migration, plate-out
stabilize poly(methyl methacrylate) [56]; when 5. Compatibility with other additives and
colorlessness is important, oxalanilides pigments
(OA-UVA 1) are employed. Oxalanilides are 6. Effect on transparency
also used in unsaturated polyesters and polycar- 7. Effect on lightfastness
bonates, but a satisfactory solution still has to be 8. Effect on electrical insulation
found to the problem of light-induced yellowing 9. Fogging (especially for automotive interior
in polycarbonates. parts)
Vol. 27 Plastics, Additives 639

10. Occupational hygiene and approval as indi- ates) naphthenates, or phenolates. The Ba – Cd
rect food additives types are most effective, followed by Ba – Zn,
11. Easy handling and costs and Ca – Zn. They must always be reinforced
with costabilizers. Recent developments include
Combinations of stabilizers and costabilizers a zinc glycinate H2NCH2COOZnOOCCH3 [59],
are normally used to obtain optimal effects. which is also used in combination with barium
Many systems are employed in industry; PVC or calcium carboxylates.
stabilization is discussed in detail in [57], [58].
Organotin Stabilizers are characterized by
their tin content (4 – 25 %). They are classified
4.2. Chemical Classes as those containing sulfur (tin mercaptides, i.e.,
thiolates) and those containing none (tin carbox-
Heat stabilizers for PVC are divided into ylates). The first group are the most efficient
metal-containing and metal-free stabilizers heat stabilizers. They can be employed without
(costabilizers). costabilizers and include mainly mono- and
dialkyltin mercaptides, mercaptoacetates,
mercaptopropionates, and thioglycolates with
4.2.1. Metal-Containing Stabilizers the following formula:
The strengths and weaknesses of the main metal- ðR1 Þn SnðSR2 Þ4n
containing heat stabilizer classes are summarized
in Table 6. where n ¼ 1 or 2; R1 ¼ methyl, n-butyl, n-octyl,
or n-dodecyl; and R2 is, for example,
Lead Stabilizers include basic lead carbo- CH2COO-alkyl, CH2CH2COO-alkyl, or
nates (e.g., x PbO  PbCO3), sulfates, phosphites, CH2CH2OOC-alkyl. The alkyl group is often
stearates, maleates, phthalates, salicylates, and isooctyl.
silicates, as well as neutral lead stearate ‘‘Methyltin stabilizers’’ (R1 ¼ methyl) offer
Pb(OOCC17H35)2. They have an excellent better thermal stability than products containing
cost – performance ratio. higher alkyl groups, because the latter suffer
thermal b-elimination. Cyclic dialkyltin sulfides
Mixed Metal Stabilizers include systems are also employed, especially in multicomponent
of barium – cadmium, barium – zinc, and calci- additive systems.
um – zinc compounds, mainly carboxylates Most of the sulfur-free organotin stabilizers
(e.g., stearates, laurates, oleates, or alkylbenzo- are dibutyltin or dioctyltin carboxylates,

*
Table 6. Strengths and weaknesses of metal-containing heat stabilizers for PVC

Mixed metal stabilizers

Ba – Cd Ba – Zn, Tin mer-

Property Lead stabilizers Ca – Zn captides Tin carboxylates

Versatility    þ þ
Lubricant action  þ þ  
(þ for stearates)
Migration/plate-out þ  þ/ þ þ
Transparency of PVC    þ þ
Light stability þ þ   þ
Sulfur staining   þ  þ
Odor þ  þ  þ
Electrical insulating properties,
water absorption þ    
Toxicology, food approval in
some cases   þ þ 
*
þ No problems, often beneficial effect;  Problematic
640 Plastics, Additives Vol. 27

especially cyclic maleates, semiesters of maleic Double-bond formation occurs in preference

acid, or laurates. to oxidation of the radical sites to peroxy radicals
in the presence of oxygen. Elimination of HCl
Antimony Stabilizers include antimony with the formation of polyene structures con-
thiolates [e.g., Sb(SCH2COOR)3]. tinues. Products containing 6 – 7 conjugated
double bonds are colored.
Ionic mechanisms have also been proposed,
4.2.2. Metal-Free Stabilizers but these are less prominent at higher tempera-
ture. The formation of carbenium chlorides in
These costabilizers always have to be used in the polymer backbone results in deepening of the
conjunction with metal-containing stabilizers. color (‘‘halochromy’’). Thermooxidative pro-
The most important costabilizers follow. cesses accelerate degradation.
Stabilizers neutralize labile chlorine atoms
Phosphites. Tris(nonylphenyl) phosphite by reacting with them to form more stable com-
and mixed aromatic – aliphatic phosphites, such pounds:
as diphenyldecyl phosphite, are often used.

Epoxy Compounds. The principal epoxy

stabilizers are epoxidized plant oils, chiefly ep-
oxidized soybean oil.

Polyols. include pentaerythritol, trismethy-

lolpropane, and tris(hydroxyethyl) cyanurate.

Other Costabilizers include b-aminocroto-

nates, dihydropyridines, and 1,3-diketones.

4.3. Mechanism of Action

The primary step in the thermal degradation of

PVC is free-radical formation by the elimination
of activated chlorine atoms, such as those on allyl
groups or in tertiary positions. The chlorine
atoms attack the polymer, resulting in hydrogen
abstraction (formation of HCl) and double-bond
formation [60].

The exchange reactions (Eq. 3 and 4) (Frye –

Horst theory [61]) form the basis for many
mechanistic analyses. The metal stabilizers are
finally converted to chlorides: R2SnCl2, ZnCl2,
CdCl2, and PbCl2. The metal stabilizers also react
with and neutralize hydrogen chloride, which
would catalyze further PVC degradation.
The metal chlorides CdCl2 and especially
ZnCl2 are, however, Lewis acids and have a
destabilizing influence because they catalyze
further elimination of HCl. Consequently,
Vol. 27 Plastics, Additives 641

although initial stabilization is excellent, further are heated in a furnace (e.g., to 180 – 200  C),
heating leads to a sudden deep coloration of the and the specimen color is observed as a function
PVC (‘‘zinc burning’’). The remedy is to exploit of time. In the dynamic test, PVC is treated in a
the synergism of mixed metal stabilizers. Cad- two-roll mill, Brabender plastograph, or extruder
mium and zinc carboxylates are always used in at specified temperatures. Samples are with-
combination with barium or calcium carboxy- drawn after various times or numbers of extrusion
lates, which exchange anions with zinc chloride passes and pressed into films, whose color is then
and cadmium chloride. The zinc and cadmium determined (usually via the yellowness index).
stabilizers are therefore regenerated, with the Because color development in PVC is fairly
formation of barium and calcium chlorides which rapid, these tests (i.e., heat treatment) seldom
do not enhance PVC degradation. Barium and require more than a few hours. The profile of the
calcium carboxylates also react preferentially yellowness index curves reflects the effects of
with HCl. stabilizers, particularly with regard to short-term
No catalytic effect on degradation is observed and long-term stabilization, and improvements
with lead chloride and (di)alkyltin chlorides; the due to costabilizers.
alkyl groups in the latter compounds have a The effect of heat stabilizers on the processing
deactivating action. For the effects of metal and service qualities of PVC is the concern of
chlorides, see [62], [63]; for the mechanism of extensive testing programs [67].
organotin stabilizers, see [64].
Costabilizers, such as polyols [63] and epoxy
compounds, also neutralize harmful metal chlor- 4.5. Uses
ides and improve long-term stabilization with
calcium – zinc stabilizers. b-Diketones [65], The choice of stabilizer system depends on the
[66] and dihydropyridines, in contrast, improve processing methods used (extrusion, injection
the initial color stabilization; the dihydropyri- molding, calendering, plastisol application), the
dines hydrogenate polyene sequences and there- intended uses of the PVC, and compatibility with
by shorten their length. Tin mercaptides and the other additives. Technologies and regulations
thiols formed by their reaction with HCl can also vary greatly. The following survey can therefore
react with polyene double bonds. The double give only general indications and trends. For
bond in tin maleates can react with polyenes further details, see the producers’ literature.
(Diels – Alder addition):
Rigid PVC. Solid stabilizers or stabilizer
blends are generally preferred for rigid PVC.
Organotin stabilizers have found wide use be-
cause processing conditions are more severe than
those for flexible PVC.
Window Frames and Sidings. Tin mercap-
tides are used in the United States; in Europe a
shift from BaCd stabilizers has been observed
Finally, alkyltin mercaptides and phosphite into CaZn costabilizer systems via BaCdPd
costabilizers act as hydroperoxide decomposers, and Pb formulas. Tin carboxylates are also used,
thus protecting against oxidative degradation. especially for transparent or colored frames,
because of their good weather resistance.
Pipes, Including Water-Supply Pipes. Tin
4.4. Test Methods mercaptides are used in the United States. Lead
stabilizers predominate in Europe (except
The most important test methods are based on France) and Japan.
static and dynamic heating. Analytical methods Beverage Bottles and Bottle Caps. The PVC
such as the determination of dehydrochlorination is stabilized with food-approved tin mercaptides
at 180 – 200  C are also common. or CaZn costabilizer systems containing epox-
In the static heating test, films produced in a idized soybean oil, 1,3-diketones, or polyols as
two-roll mill or plastisols applied to a substrate costabilizers.
642 Plastics, Additives Vol. 27

Flexible PVC. Most of the stabilizers used such as granules, flakes, or ‘‘small bags’’ are
for flexible (plasticized) PVC are in liquid form; preferred. ‘‘One-pack’’ systems, which contain
BaCd and BaZn systems occupy the leading primary and secondary stabilizers preblended
position, with a trend toward cadmium-free sys- with lubricants and other additives, are widely
tems including CaZn products, e.g., in foils, used. Most producers offer broad assortments,
films, leather imitates (shoes, automotive inter- with individual products that are continually
iors), hoses, and floor coverings. Lead stabilizers being modified and tailored to specific applica-
are used in electrical cables. tions. Among the nonmetallic costabilizers,
epoxidized soybean oil holds a dominant position
Stabilizer Content. Heat stabilizer contents with more than 100 000 t/a used worldwide
of 0.3 – 5 % are common. Levels of organotin in PVC.
stabilizers are at the low end of the range Table 8 lists the most important producers and
( 2.5 %), mixed metal stabilizers in the middle, trade names of PVC heat stabilizers.
and lead stabilizers for cable insulation at the
high end. Phosphite or 1,3-diketone costabilizers
are generally used below 0.5 %, whereas epoxi- Table 8. Producers of PVC heat stabilizers
dized soybean oil is added in concentrations of
Producer Trade name Type*
5 % or higher.
Acima Metastab Sn, Me
Adeka Argus Mark Me, Pb, C, Sn
Legal Aspects. Some countries place strict Akishima Chemicals Me, Sn
limits on the use of certain stabilizer classes; for Akzo Interstab, Stanclere, Me, Sn, Pb, C
example Sweden and Japan restrict the use of Estabex
cadmium stabilizers. Similar provisions are un- BASF Sicostab Me
Bleiberger Bergwerks Austrostab Pb, Sn, Me, C
der discussion for the EC. Other broad limits Union
apply to lead stabilizers in drinking-water pipes Cardinal Chemicals CC Sn
in France and the United States. Chemson Naftovin, Strandex Pb, Me, Sn
Stabilizers for products that come in contact Ciba-Geigy Irgastab, Reoplast Sn, Me, C
Commer Prosper Sn, Me, Pb, C
with food (e.g., beverage bottles, packaging CWM O. B€arlocher B€arostab, Okstan Me, Sn, Pb, C
films) must be officially approved as indirect Ferro Corporation Therm Chek Me, Sn, C
food additives. Many octyltin and dodecyltin Hammond Lead Products Halstab Pb
mercaptides [e.g., di-n-octyltin bis(isooctylthio- Hebron Vinstab Sn, Me, Pb, C
Henkel Edenol, Stabilox, C
glycolate)], most of the CaZn stabilizers, and Stabiol
many costabilizers (especially stearylbenzoyl- Hoechst Hostastab Sn, C
methane, dihydropyridine and epoxidized oils) Katsuta Kako Advastab Me, C, Sn
have such approval. Kemichrom Kemistab Sn, Me, Pb, C
Kyodo Chemicals Sn, Me
Lagor Lastab, Synesol Me, Sn, C
Meister Meister Sn, Me, C
4.6. Economic Aspects Morton Thiokol Advastab Sn
M & T Chemicals Thermolite Sn, Me, Pb, C
Nissan Ferro Organic Therm Chek Me
Table 7 lists estimated 1990 market volumes for Chem.
metal-based heat stabilizers that are used as Nitto Kasei Sn
solids, pastes, or liquids. Dust-free solid forms Plastics Specialities & Me
Technologies
Reagens Reatinor, Reablend Sn, Me, Pb, C
Table 7. Estimated market volume of PVC heat stabilizers in Rhône-Poulenc Rhodiastab C
1990 (103 t) Sakai Kagaku Me, C, Sn
Sankyo Organic Gosei Stann Sn
Region Tin Lead Mixed metal Total Swedstab Swedstab Sn, Me, C
Synthetic Products Synpron Sn, Me
United States 20 10 25 55 Tinstab SA Tinstab Sn, Me, C
Western Europe 10 50 40 100 Tokyo Fine Chemicals Embilizer Sn
Japan 10 30 15 55 R. T. Vanderbilt Vanstray, Barostab Me
Other 10 30 15 55 Witco Corporation Mark Me, Sn
Total 50 120 95 265 *
C¼costabilizer; Me¼mixed metal; Pb¼lead; Sn¼organotin.
Vol. 27 Plastics, Additives 643

5. Lubricants, Slip, Antiblocking, additive concentration, the presence of other

and Mold-Release Agents lubricants, and the processing temperature. Many
products also perform multiple functions: exter-
5.1. Purpose and Requirements nal lubricants are often effective as mold-release
[68], [69] or slip agents. Carefully matched combinations
of additives are often required. This group of
Lubricants (! Lubricants and Lubrication), additives must also comply with standards of
slip, antiblocking, and mold-release agents odor and taste, migration behavior, product sta-
(! Release Agents) control the frictional and bilization [70], and thermal stability.
adhesive properties of plastics during processing Lubricants and related compounds may have
and in service. disadvantageous effects on some product prop-
Lubricants also improve the dispersion of erties. Internal lubricants can act as plasticizers
pigments and fillers in plastics. Uniform colors and thus reduce the heat distortion temperature.
can be obtained by breaking up agglomerates in External lubricants can reduce transparency and
pigment preparations. Better dispersion of fillers impair the printability, cementability, and weld-
(e.g., talc) improves flow limits and material ability of plastics. These additives also affect
properties. mechanical properties, especially in case of over-
lubrication, which causes inhomogeneities due to
Internal Lubricants reduce friction between inadequate fusion of the material.
polymer particles and molecules during the melt-
ing (plastication) of plastics and transport of the
melt. They thus reduce energy consumption on 5.2. Chemical Classes
plastication, lower melt viscosity, improve flow
properties, increase output of processing machin- Many lubricants are amphoteric compounds con-
ery, and allow processing under less stringent taining both a long hydrocarbon chain and polar
conditions. groups (e.g., hydroxyl, ester, or acid groups).
Lubricants are characterized by their molecular
External Lubricants reduce the friction and mass, acid or hydroxyl number, saponification
adhesion of polymer melts on hot metal surfaces number, metal content, melting or dropping
of processing machinery (e.g., extruder screws point, cold-setting temperature, thermal stability,
and cylinders, rolls). This reduces abrasion be- volatility, density, viscosity, and (for solid
tween the polymer melt and the metal, and im- agents) particle size. The action of a lubricant
proves melt flow. It also improves the gloss, depends on its polarity. Polar molecules act as
smoothness, and regularity of the surface of the internal lubricants in polar polymers such as PVC
plastic. and as external lubricants in nonpolar polymers
such as polyolefins, and vice versa. The polarity
Mold-Release Agents prevent the adhesion is strongly influenced by the length of the hydro-
of molded plastics to metal cooling rolls and carbon chain. Lubricants can be classified as fatty
molds. Slip agents improve the frictional quali- acids and their derivatives (C12 – C22 chains),
ties of finished plastic surfaces (e.g., bearings and montanic acids and their derivatives (C28 – C32),
gears) and prevent adhesion between stacked paraffins (C20 – C70), and polyolefin waxes (mo-
films. Antiblocking agents prevent adhesion be- lecular mass 2000 – 10 000).
tween film layers on rolls or in stacks when The substances of greatest practical impor-
pressure and heat are applied. tance are listed below; for further details, see
! Lubricants and Lubrication.
Antislip Agents (adhesion promoters) impart
limited tack to finished articles to reduce slip (e. Fatty Acids, Fatty Alcohols, and Their Deri-
g., between filled bags made of plastic films). vatives comprise the following groups:
It is not always possible to assign a particular
product to one of the above classes. For example, 1. Stearic, 12-hydroxystearic, palmitic, and be-
the boundary between internal and external henic acids
lubricants depends on the type of polymer, the 2. Cetyl and stearyl alcohols
644 Plastics, Additives Vol. 27

3. Metal stearates (Zn, Ca, Pb, Al, Mg, and Na) 5.3. Mechanism of Action
4. Butyl stearate, tridecyl stearate, glycerol
monostearate (GMS), glycerol monoricinole- The friction-lowering property of lubricants is
ate, glycerol monooleate, glycerol tristearate, due to their long hydrocarbon chains (> C12).
glycerol tri-12-hydroxystearate (hydrogenat- The lubricating effects depend on interactions
ed castor oil), trimethylolpropane tristearate, between the lubricant and the polymer matrix
and pentaerythritol tetrastearate (solubility of the lubricant in the polymer) and
5. Distearyl adipate, distearyl phthalate, cetyl on the association between the lubricant and the
palmitate, cetyl stearate, stearyl stearate, and metal surfaces. Unlike plasticizers, which are
behenyl behenate completely soluble in the polymer, lubricants
6. Isostearamide, oleamide, erucamide, ethylene should have only limited solubility; this is en-
bisstearylamide (EDS or ‘‘amide wax’’) sured by their amphoteric character.
7. Oligomeric fatty acid esters (‘‘complex fatty
acid esters’’) are also used. These are obtained Internal Lubricants [71] have a relatively
by polycondensation of dicarboxylic acids high affinity for polymers. Polar lubricants in,
(e.g., adipic acid), polyols (e.g., pentaerythri- for example, PVC are either dissolved in or
tol), and monocarboxylic acids (e.g., stearic strongly bound to the surface of the associations
acid). They may be partially saponified or of polymer molecules that occur in the plastic
may contain calcium. state. Typical effects are a lowering of the soft-
ening temperature due to swelling, a reduction in
Montanic acids and their derivatives (montan melt viscosity, and frictional damping between
waxes). Montanic acids are obtained from lig- polymer particles. Good internal lubricants have
nite and consist of mixtures of C28 – C32 acids. high saturation limits and haze points.
Derivatives include calcium montanates, sodium
montanates, and esters with ethylene glycol, External Lubricants are strongly associated
butanediol, glycerol, or pentaerythritol. to the metal surfaces of processing equipment or
form discrete phases within the polymer melt.
Paraffins may be derived from petroleum
They only have a low affinity for the polymers.
(straight-chain members are solids, branched- Typical effects are a reduction in adherence to the
chain members are liquids) or are synthetic metal and in friction between polymer particles,
(Fischer – Tropsch) paraffins.
which leads to slower plastication. External lu-
bricants often cause haze. Overlubrication must
Polyolefin Waxes. The most common poly-
be avoided because some adhesion to the metal
olefin waxes are polyethylene waxes with
is necessary for conveyance of the melt in the
branched and linear structures; partially crystal-
extruder and also in calendering.
line polypropylene waxes are less common. Polar
polyethylene waxes are obtained by oxidation;
they have acid numbers of ca. 20 – 70. Mold-Release Agents form a film between
the metal surface and the cooled plastic. Slip
Other Chemical Classes. Fluorinated poly- agents migrate to the plastic surface, where their
mers, chlorinated paraffins, silicones, graphites, hydrocarbon chains act as a lubricant. Antiblock-
and other substances are used as lubricants and ing agents slightly roughen the film surface so
related compounds. Silica gel, chalk, and other that air is trapped between stacked layers. Anti-
minerals are employed as antiblocking agents slip agents artificially create surface roughness
and slip aids. where nonlubricating particles incorporated in
This article does not cover externally applied the melt protrude from the film.
mold-release agents (e.g., waxes, fluorinated
polymers, silicones, and metallic soaps), which
are sprayed or brushed onto mold surfaces. These 5.4. Test Methods
methods are used chiefly with thermosetting
resins (e.g., polyurethane, unsaturated polyester, Methods based on practical applications are
epoxy). applied to lubricant testing. One of the most
Vol. 27 Plastics, Additives 645

5.5. Uses

The main application of lubricants is in PVC

(ca. 50 %), followed by styrene polymers, poly-
olefins, engineering thermoplastics, and thermo-
plastic elastomers.

Rigid PVC always requires lubricants for

processing (usual content 1 – 4 %), and lubricant
combinations (preformulated systems) are often
employed. Selection of lubricants is dictated by
the type of heat stabilizer used: stearic acid with
Figure 6. Schematic plastogram of PVC with lubricant lead stabilizers; 12-hydroxystearic acid with bar-
(Brabender Plasticorder) ium – cadmium stabilizers (to reduce plate-out);
glycerol monostearate, montan waxes, or oxi-
dized polyethylene waxes with tin stabilizers;
and complex fatty acid esters with calcium –
important is the plastograph (e.g., the Brabender zinc stabilizers.
Plasticorder). The formulated plastic powder is Fatty acid esters, calcium stearate, and fatty
placed in a kneading chamber at a preset tem- alcohols are typical internal lubricants. Montan
perature (e.g., 140 – 160  C) and plasticated by waxes, amide waxes, paraffins, oxidized poly-
a twin-shaft device running at constant speed. ethylene waxes, and fatty acids act as external
The torque is plotted as a function of time lubricants. Heavy-metal soaps and complex fatty
(Fig. 6). The curve passes through a maximum acid esters fall between the two types. Lubricants
torque value Tmax, marking the onset of plastica- allow processing under gentler conditions and
tion in the powder mixture. It then declines to thereby contribute to stabilization. A combina-
a minimum Tmin, followed by an increase to a tion of calcium stearate as internal lubricant,
second maximum Te as a result of growing paraffin wax as external lubricant, and oxidized
friction. Plastication is complete at Te. The time polyethylene wax as mold-release agent has been
between Tmax and Te is called the plastication used with success for PVC pipes.
time tg. The test is used to establish suitable
ratios of internal and external lubricants. For Flexible PVC requires less lubricant (ca.
example, a shorter tg or an increase in the ratio 0.5 %). Liquid types,such as glycerol monooleate
(Tmax  Tmin)/tg indicates internal lubrication. or paraffin oils, are used. Amide waxes serve as
As the hydrocarbon chain in the lubricant be- antiblocking agents.
comes longer, the maximum kneading resistance The flow behavior of ABS, SAN, and polysty-
declines. rene can be improved with butyl stearate, glyc-
Other tests employ extrusiometers (measure- erol monostearate, fatty acid esters, paraffin oils,
ment of polymer melt temperature and pressure oxidized polyethylene waxes, and montan
in the extruder cylinder and at the die), capillary waxes. Zinc stearate and amide wax (0.1 –
viscometers (quantity of material discharged per 2 %) are used as mold-release agents.
unit time at constant pressure and temperature) The calcium stearate used as an acid radical
[72], or roller mills (time that elapses between scavenger is often sufficient for polyolefins.
charging and adhesion of the polymer sheet on Neutral polyethylene and polypropylene waxes
the rolls). In the spiral test, material is injected are added to pigment preparations for polyethyl-
into a spiral mold and the distance the material ene and polypropylene. Talc-filled polypropyl-
travels in the runner is measured. ene can contain ca. 0.5 % of partially saponified
Slip and blocking effects are studied in skid montan wax. A suitable mold-release and slip
and adhesion tests with films (e.g., ASTM agent for films is 0.1 – 0.3 % of a fatty acid amide
D 1893 or D 3354). Haze and surface gloss in polyethylene or of erucamide in polypropyl-
measurements are an important component of ene. Finally, 0.05 % of fluorinated polymers can
all lubricant tests. be added to LLDPE films to combat melt fracture
646 Plastics, Additives Vol. 27

(a surface defect occurring at high viscosity and Table 9. Producers and trade names of lubricants and related
compounds
resulting from the alternating wall adhesion and
slip of the extrudate). Highly effective slip aids Manufacturer Trade name
for polyolefin films include micronized synthetic
Abril Industrial Waxes Abril Wax
silica gels. Akzo Chemicals Dopral, Interstab, Armoslip,
For engineering thermoplastics [polycarbo- Aramid
nates, polyamides, poly(ethylene terephthalate) Allied Signal AC Polyethylene
(PETP), poly(butylene terephthalate) (PBT)], Ashland Chem.
Astor Wax Comboloob
thermally stable pentaerythritol esters of fatty Axel Plastics Res. Labs. Mold Wiz
acids are preferred; they have a better transpar- CWM O. B€arlocher B€arolub
ency than montanate esters. Amide wax can also BASF Sicolub, Wachs BASF
serve as a mold-release agent. Filled thermoplas- Dr. T. B€ohme Tebestat
Chemson Naftolube, Naftozin, Listab
tics represent a broad field for lubricants. Ciba-Geigy Irgawax
Because most lubricants are derived from Corriel Lubriol, Synthewax,
natural sources, they are often approved for food Glycmonos
packaging products. Commer Vinlub
Croda Universal Crodamid, Crodacid
Deer Polymer
Du Pont Zonyl, Viton
5.6. Economic Aspects Durham Chemicals Durolube
Eastman Epolene, Myverol,
Myvaplex
Current worldwide consumption of lubricants Th. Goldschmidt Tego, Tegin
and related compounds is ca. 130 000 – Grace Sylobloc
140 000 t, with Western Europe, the United C. P. Hall
States, and the rest of the world accounting for Harcros Chemicals Harochem, Harowax,
Harogel, Lankroplast
a third each. Consumption is equally divided Harwick Chemicals Lubrox, Lubrex
between the five following groups: fatty acids Henkel Loxiol, Loxamid
and esters, metallic soaps, amide waxes, paraffin Hoechst Hostalub, Hostamont,
and polyethylene waxes, and miscellaneous Hoechst Wachse
H€uls Vestowax
types. Humko Chemicals Kemamide, Kemester,
Table 9 lists some important producers and (division of Witco) Mold Pro, Micro-ken
trade names of lubricants and related com- ICI Atmer
pounds. The number of products on the market Kao Corporation
Kemichrom Kemfluid
is relatively large because new formulations and Lion Akzo
easy-to-handle forms are continually appearing. Lonza Glycolube
Most products for PVC are sold to converters; 3M Dynamar
those for other polymers are often sold to the Marabushi Oil Chemicals
Mathe Co. Coad
polymer producers. Mazer Chemicals (division
of PPG)
Morton Thiokol Advawax
6. Flame Retardants [73–78] M & T Chemicals Stavinor
New Japan Chemical Co.
See also ! Flame Retardants, chap.2 Nippon Oil & Fats
Nitto Kasei
6.1. Purpose and Requirements Reagens Realube
Rohm & Haas
Rousselot
The replacement of classical materials by com- Sakai
bustible plastics in buildings, equipment, and Speciality Products Zn-Stearate
vehicles creates a fire risk. Flame retardants are Struktol Co. Polydis TR
used to combat this danger. A useful measure of Swedstab Swedlub, Swedstab
Tonnan Kagaku Kogyo
flammability for plastics is the limiting oxygen Unichema Chemie Unislip, Uniwax, Estol,
index (LOI), which denotes the volume fraction Priolube, Prifrac, Pristerene
of oxygen in an oxygen – nitrogen mixture
that just supports combustion of a well-defined
Vol. 27 Plastics, Additives 647

specimen under standard conditions. A high LOI plastics modified with these additives are still
indicates a low flammability. The LOI values for combustible.
the most important plastics follow: In many cases and especially at high concen-
trations, flame retardants lower the quality and
Polyoxymethylene 15.5
increase the price of a plastic. They are therefore
Polyethylene 17.3 used only when mandated. Selection is deter-
Poly(methyl methacrylate) 17.5 mined by the effectiveness and price of the flame
Polypropylene 17.6 retardant, as well as the processibility of the
Polyurethane 17 – 19
Polystyrene 18.0
plastic, and influences on its mechanical, optical,
Unsaturated polyester 18.5 and electrical properties. Interactions with other
ABS 18 – 19 additives (e.g., light stabilizers) must also be
Epoxy resin 19.0 considered.
PBT 21.5
Polyamide 12 21.6
PETP 22.0
Polycarbonate 23 – 25
6.2. Chemical Classes
Polyamide 6 23 – 26
PVC, flexible 24 – 25 Flame retardants may be inorganic substances,
Poly(phenylene oxide) – polystyrene 24 – 25 halogenated organic compounds, organophos-
Polyamide 66 24 – 26
PVC, rigid 40 – 45
phorus compounds, or other organic substances.
Polytetrafluoroethylene 95.0 They are further classified as additive or reactive.
Reactive flame retardants are incorporated
into the polymer molecule by copolymerization,
Flame retardants in plastics affect ignitability, cross-linking, or grafting.
combustion rate, heat release, fuel contribution,
smoke evolution, and the formation of toxic or Inorganic Flame Retardants. Producers
corrosive gases. The significance of these para- and trade names are summarized in Table 10.
meters depends on the situation. Although flame
retardants can be especially effective in the early Aluminum Trihydroxide , Al(OH)3, and
stages of a fire and can reduce flammability, magnesium dihydroxide, Mg(OH)2, [79] are the

Table 10. Producers and trade names of inorganic flame retardants

Compound CAS registry no. Producer (trade name)

Aluminum trihydroxide, Al(OH)3 [21645-51-2] Aluchem; BA Chemicals, Alcan Aluminium (Baco Superfine, Ultrafine);
Alcoa (Hydral, Flameguard); Atochem; Kaiser Aluminium; Martinswerke,
Lonza (Martinal); Reynolds Metals; Solem Industries, J. M. Huber
(Micral, Zerogen); Vereinigte Aluminium Werke (Apyral); Showa
Aluminium Industries; Sumitomo Aluminium Smelting
Magnesium dihydroxide, Mg(OH)2 [1309-48-4] Dead Sea Bromine (FR-20); Kyowa Chemicals; Lonza (Magnifin);
Morton Thiokol (Versamag); Solem Industries, J. M. Huber (Zerogen);
Veitscher Magnesitwerke
Antimony trioxide, Sb2O3 (some as [1309-64-4] Anzon (Firebloc, Envirostrand, Oncor); Asarco; Laurel Industries
concentrate or in wetted form) (Fire Shield); M & T Chemicals (Thermoguard); Amspec Chemical;
BA Chemicals (Timonox)
Antimony pentoxide, Sb2O5 [1314-60-9] Nyacol Products (Nyacol)
Sodium antimonates, M & T Chemicals (Thermoguard)
e.g., Na2Sb2O6  x H2O
Zinc borates, e.g., [12536-65-1] Borax Holdings; Climax Performance Materials (ZB-223); US Borax &
4 ZnO  6 B2O3  7 H2O Chemicals (Firebrake ZB)
Barium metaborate, e.g., Buckman Laboratories (Busan)
BaB2O4  x H2O
Ammonium polyphosphate, [68333-79-9] Albright & Wilson (Amgard MC); Hoechst (Exolit); Monsanto (Phos-Chek);
(NH4PO3)n (some coated or Great Lakes (Char Guard 329, CN 1197)
encapsulated, some in systems with
flame retardants containing N)
Red phosphorus [7723-14-0] Albright & Wilson (Amgard CRP); Hoechst (Exolit 405)
648 Plastics, Additives Vol. 27

largest group of flame retardants in terms of Other Inorganic Flame Retardants include
consumption. Particle size varies from 1 to iron oxides (Fe2O3 and Fe3O4); hydrated calcium
30 mm. High concentrations (40 – 60 wt %) of and magnesium carbonates; bismuth oxides and
these additives are required and are associated carbonates [84]; boric acid and borates; zinc
with a severe impairment of mechanical proper- hydroxystannate [ZnSn(OH)6], zinc stannate
ties. To overcome this, products coated with (ZnSnO3), and other zinc compounds [85]; and
coupling agents (e.g., silanes, fatty acid esters) mineral substances that decompose endothermi-
are recommended. The coating may, for exam- cally at certain temperatures to release water or
ple, improve the impact strength of the modified noncombustible gases. Smoke-inhibiting addi-
plastic or reduce the viscosity of prepolymers. tives for PVC, unsaturated polyesters, or poly-
Aluminum and magnesium hydroxides often urethanes include calcium carbonate, tin oxides,
suppress smoke evolution. Use is limited by their copper oxide, molybdenum trioxide, and ammo-
thermal stability (dehydration); Al(OH)3 decom- nium molybdate.
poses above ca. 200  C, and Mg(OH)2 above
300 – 340  C. Halogenated Organic Flame Retardants.
Halogenated compounds are effective flame re-
Antimony Compounds. Antimony trioxide, tardants, especially in conjunction with antimony
Sb2O3; antimony pentoxide, Sb2O5; and sodium trioxide. They can therefore be used in low
antimonates (e.g., Na2O  Sb2O5  x H2O) are concentration so that they do not greatly affect
largely used as synergists with halogenated or- product properties. A drawback is the fact that
ganic flame retardants or in PVC. In the absence corrosive gases (HBr, HCl) are always produced
of halogen compounds they have little effect. in the event of fire and can cause secondary
Antimony trioxide is sold in various purities, damage. Light stability of the plastic is also
whitenesses, and grain sizes (mainly 1 – 3 mm, reduced, especially by brominated compounds.
down to <1 mm for special grades). Antimony The most important members of this group are
pentoxide is available in colloidal form brominated aromatics, above all decabromodi-
(0.03 mm). Because of occupational health issues phenyl oxide and polymeric compounds. Some
relating to antimony trioxide dust, nondusting important producers and trade names are listed
preparations are preferred (i.e., concentrated in Table 11. Aliphatic bromine compounds are
masterbatches containing ca. 80 % of active often more effective but less thermally stable.
agent, granules, or wetted grades). This disadvantage is partially offset in brominat-
ed neopentyl structures that do not have hydro-
Zinc Borates [80] often serve as a partial gen atoms in the a-position to the bromine.
replacement for antimony trioxide, giving some Hexabromocyclododecane is an example of a
advantages in suppression of smoke evolution, brominated cycloaliphatic compound; tetrabro-
afterglow, weaker pigmentation, and lower cost. mobisphenol A is the most important reactive
Combinations with aluminum trihydroxide are type.
also employed. Negative effects on the stability Chlorinated flame retardants (Table 12) are
of halogen-containing plastics must be only about half as effective as brominated ones
considered. because of the higher bond energy of chlorine.
Chlorinated paraffins and chlorinated cycloali-
Ammonium Polyphosphate, (NH4PO3)n, is phatics are mainly used [86]. Fluorine and iodine
included in intumescent systems [81], [82] that compounds are not employed as flame
contain polyols and melamine derivatives retardants.
(! Flame Retardants). The products are also
marketed in coated or microencapsulated form Organophosphorus Flame Retardants.
to reduce water absorption, for example. Important products and trade names are listed in
Microencapsulated or inertized red phospho- Table 13.
rus is a very effective flame retardant that can be The most important organophosphorus
processed at up to 280  C [82], [83]. Its draw- flame retardants are halogen-free triaryl phos-
backs are a dark color and potential handling phates. Phosphonates (e.g., dimethyl methylpho-
hazards. sphonate), phosphine oxides, and halogenated
Vol. 27 Plastics, Additives 649

Table 11. Producers and trade names of brominated organic flame retardants

(Continued )
650 Plastics, Additives Vol. 27

Table 11 (Continued )
Vol. 27 Plastics, Additives 651

Table 11 (Continued )

phosphate esters and phosphonates are also used. 5. Alkali-metal salts of organic sulfonates for
Advantages include low corrosivity of the com- polycarbonates [89]
bustion gases, lack of effect on polymer transpar- 6. Ferrocene as a smoke inhibitor in PVC
ency, and suppression of afterglow. Drawbacks
include volatility, sensitivity to hydrolysis,
and negative effects on the heat distortion tem- 6.3. Mechanism of Action
peratures of plastics. Cyclic organophosphorus
compounds (phosphorinanes, phosphazenes) Three elements are essential for a fire: heat, fuel,
overcome some of these problems. and air (oxygen) (Fig. 7). When heated, plastics
undergo pyrolysis, forming characteristic degra-
Miscellaneous Organic Compounds. Or- dation products, some of which appear as smoke
ganic additives occasionally used in flame retar- whereas others serve as fuels that can be ignited
dant systems or for special types of plastics once they are mixed with air. Oxidative combus-
include the following: tion reactions in the gas phase (the ‘‘fire’’) are
strongly exothermic. Thus, large amounts of
1. Polyols (e.g., pentaerythritol) for intumescent thermal energy are returned to the plastic and to
systems [81] the surroundings. Pyrolysis and the associated
2. Nitrogen-containing compounds (e.g., mela- fuel generation are thereby accelerated, and
mine or melamine cyanurate), often com- the fire propagates. Flame retardants interfere
bined with (NH4PO3)n with these processes by one or more chemical
3. Silicones [87] as smoke inhibitors and impact or physical mechanisms [90].
modifiers when high concentrations of
Al(OH)3, Mg(OH)2, or (NH4PO3)n are used Fuel Dilution. Noncombustible products
as flame retardants (CO2, H2O) are generated by thermal decompo-
4. Free-radical formers (e.g., dicumyl peroxide sition of the flame retardant and released into
or 2,3-dimethyl-2,3-diphenylbutane) together the gas phase. Examples of such flame retardants
with brominated compounds, especially in are Al(OH)3, Mg(OH)2, hydrated carbonates,
expandable polystyrene [88] boric acid, and borates. The decomposition
 652 Plastics, Additives Vol. 27

temperature of the flame retardant must be com-

patible with the processing temperature and
pyrolysis temperature of the plastic.

Endothermic Action. If the pyrolytic de-

composition of the flame retardant is endother-
mic, it can absorb part of the energy released
during combustion. This mechanism often ac-
companies fuel dilution.

Protective Coating. The flame retardant

forms a protective coating on the surface of the
pyrolyzing plastic. It acts as thermal insulation
and a barrier to oxygen, and also prevents com-
bustible pyrolysis products and smoke particles
from escaping into the gas phase. Most of the
inorganic and organophosphorus flame retar-
dants function by this mechanism. The protec-
tive layer can be glassy or have a porous carbon
structure (intumescent char). In the latter case,
the flame retardant system includes components
that are responsible for char formation (e.g.,
polyols and phosphates) and expansion (e.g.,
melamine derivatives) [81], [91].

Pyrolysis Modification. Pyrolysis of the

plastic can be chemically modified, for example,
by dehydration in cellulosic polymers and poly-
urethanes or by inhibition of thermal depolymer-
ization [e.g., in poly(methyl methacrylate)] to
reduce the amount of combustible products
generated. The proportion of solid carbon resi-
Table 12. Producers and trade names of chlorinated organic flame retardants

due (char) is increased, and a noncombustible

product (e.g., water) is formed. Organophospho-
rus compounds employ this mechanism; it is
particularly effective in plastics containing ox-
ygen. This mechanism may, however, increase
smoke density.

Gas-Phase Quenching. Combustion pro-

cesses in the gas phase are highly exothermic,
free-radical chain reactions in which the fuel is
oxidized by oxygen or hydroxyl radicals, for
example:
. .
COþHO !CO2 þH þheat
. . .
H þO2 !HO þO þheat
. . .
RHþO !HO þR þheat

Flame retardants that are active in the gas

phase must neutralize the highest-energy
Vol. 27 Plastics, Additives 653

Table 13. Organophosphorus flame retardants

654 Plastics, Additives Vol. 27

electronics equipment, mining, and transporta-

tion) is covered by application-specific regula-
tions. Many test methods and standards have
been created to classify the burning behavior of
materials but there is little correlation between
them. The small-scale tests performed in materi-
als development can only simulate actual burning
behavior within limits; full-scale tests must
therefore be performed.
Test methods and standards are specified by
(inter)national standards organizations, industry
groups or organizations, and government agen-
cies. Numerous test methods are described in
[78]. See also, ! Flame Retardants, Chap. 3..
The methods encountered most frequently in
development and testing laboratories are listed
in Table 14. The relatively simple UL 94 test is
most widely used and recognized. A standard
test rod is clamped in a vertical position, and an
igniting flame is applied to the lower end twice
for 10 s. The second ignition takes place as soon
as the flame from the first ignition is extin-
guished. The rating criteria are the afterburning
time and the ignition of cotton wadding placed
under the specimen caused by molten drops
of material. The test gives a rating of V-0,
Figure 7. The Emmons fire triangle V-1, or V-2:
V-0: afterburning time of single specimen
<10 s, of five specimens with two igni-
. .
radicals, such as HO or H . Halogenated com- tions each <50 s; no ignition of wadding
pounds are especially effective in this respect. V-1: afterburning time of single specimen
Pyrolysis produces hydrogen halides or, if anti- <30 s, of five specimens with two igni-
mony trioxide is present [92], antimony halides, tions each <250 s; no ignition of wadding
which react as follows: V-2: same as V-1, but with ignition of wadding
The specimens must not be completely
. .
HBrþHO !H2 OþBr burned, otherwise no such classification is given.
. .
HBrþH !H2 þBr
. .
SbBr3 þH !HBrþBr2 Sb
6.5. Uses
Reactions of this type are less exothermic and
block free-radical chain reactions. A drawback of About 10 % of all plastics (chiefly PVC, ABS,
this mechanism is that the gas phase becomes polystyrene, unsaturated polyesters, polypropyl-
more corrosive. The smoke density may also ene, polyethylene, and polyurethanes) contain
increase due to inhibition of the combustion flame retardants. The main applications are in
reactions. building materials and furnishings (structural
elements, roofing films, pipes, foamed plastics
for insulation and furniture, wall and floor cover-
6.4. Test Methods and Standards ings); transportation (equipment and fittings for
aircraft, ships, automobiles, and railroad cars);
The use of flame-retardant materials (especially and in the electrical industry (cables; housings
in building materials, furnishings, electrical or and components for television sets, office ma-
Vol. 27 Plastics, Additives 655

Table 14. Test methods and standards (selected)

Test Standard Criteria Applications

LOI test ASTM D 2863 flammability development laboratory

Vertical test UL 94, UL 94–5 V ignitability development laboratory
dripping electrical industry
Vertical test DIN 54 332 ignitability development laboratory
floor coverings
Horizontal test ASTM D 635 burning rate development laboratory
Miscellaneous tests FAR 25 ignitability aircraft interiors
burning rate
smoke density
Horizontal test FMVSS 302 burning rate automotive interiors
Cone colorimeter ISO DP 5660 ignitability development laboratory
heat release materials in buildings
smoke
toxic gases
Epiradiator NF P 92–501 ignitability materials in buildings
burning rate
Surface spread of flame test BS 476, Parts 5 – 7 ignitability materials in buildings
burning rate
NBS smoke chamber ASTM E 662 smoke density development laboratory
aircraft interiors
Toxicity test DIN 53 436 toxicity of pyrolysis gases development laboratory
materials in buildings
Brandschachttest DIN 4102 flammability materials in buildings
heat release
Room corner test NT Fire 025 flame spread materials in buildings
smoke
toxic gases
Steiner tunnel test ASTM E 84 flame spread materials in buildings
smoke

chines, and household appliances; lamination of Acrylonitrile – Butadiene – Styrene.

printed circuits). A variety of halogenated flame retardants are
More than 90 % of the flame retardants used in used for ABS in conjunction with Sb 2O3; most
thermoplastics are of the additive type. They are common for V-0 formulations is a combina-
added before, during, or after polymerization, tion of octabromodiphenyl oxide (ca. 20 %)
but usually when the polymers are processed into and Sb2O3 (ca. 6 %). Halogen-free formula-
compounds or finished products. In the latter tions, for example with Mg(OH)2, are still
case, the retardant is often used as a highly under development.
concentrated masterbatch containing 50 – 80 %
of the agent. Expandable Polystyrene. Hexabromocy-
Reactive flame retardants are added to thermo- clododecane is used at the 3 – 5 % level to
setting resins before the cross-linking reaction. comply with building codes; 0.5 % dicumyl per-
oxide or another free-radical former is added as
Poly(Vinyl Chloride). Up to half of the synergist [88].
dioctyl phthalate plasticizers in flexible PVC can
be replaced by chlorinated paraffins or phosphate High-Impact Polystyrene. The V-0 grades
esters (e.g., triphenyl or tricresyl phosphate) [93]. contain ca. 12 % decabromodiphenyl oxide or
Other common additives are Sb2O3 (2 – 4 %) tetrabromobisphenol A together with 3 – 4 %
and Al(OH)3 (40 %). Sb2O3. Ethylene-bis(tetrabromophthalimide)
In rigid PVC, Sb2O3 (1 – 4 %) and Al(OH)3 and low molecular mass brominated polystyr-
(10 – 20 %) are employed and in some cases enes are also suitable. For V-2 grades, brominat-
zinc borate and zinc stannate. MoO3, ferrocene, ed aliphatics are used. Red phosphorus (15 %)
or CaCO3 can be used as smoke inhibitor. has been proposed for halogen-free V-0 grades.
656 Plastics, Additives Vol. 27

Polyester Resins. The use of 50 – 60 % with dimethyl methylphosphonate or halogenat-

Al(OH)3, preferably coated, is widespread. Ha- ed phosphates.
logenated reactive retardants, such as tetrabro- Thermoplastic polyurethane can be rendered
mophthalic anhydride and (for more light-stable flame resistant with brominated compounds and
grades) 2,2-bis(bromomethyl)-1,3-propanediol Sb2O3 [96] or intumescent systems.
are also employed.
Low molecular mass brominated epoxy poly- Polyamides. A variety of formulations are
mers of the F – 2000 series, together with Sb2O3, used for V-0 grades of polyamide 6 and polyam-
offer another alternative. Zinc borate or dimethyl ide 66 [97]. In systems based on brominated
methylphosphonate is also used. aromatics (15 – 20 %) and Sb2O3 (4 – 5 %),
ethylene-bis(tetrabromophthalimide) and poly-
Polyolefins. In polypropylene, 5 – 20 % tet- meric flame retardants such as poly(tribromos-
rabromobisphenol A-bis(2,3-dibromopropyl tyrene), poly(dibromophenylene ether), and
ether) is used, along with 3 – 8 % Sb2O3 [94]. F – 2000 products dominate. Dechlorane Plus is
Other halogenated compounds are also used also employed with synergists (e.g., Sb2O3, zinc
in combination with Sb2O3: ethylene-bis(tetra- borate, or Fe2O3 and Fe3O4).
bromophthalimide), ethylene-bis(dibromonor- In halogen-free systems, polyamides contain
bornane dicarboximide) or Dechlorane Plus. 7 – 10 % red phosphorus or, in the absence of
Halogen-free V-0 grades are obtained by using glass-fiber fillers, melamine cyanurate. Tests
25 – 35 % of an intumescent system based on with Mg(OH)2 are under way.
ammonium polyphosphate – pentaerythritol –
melamine derivatives or 50 – 60 % Al(OH)3 or Polyesters (PBT and PETP). The products
Mg(OH)2 [95]. used for polyesters are similar to those for
Chlorinated paraffins combined with Sb2O3 polyamides, but combinations of brominated
are used in LDPE films. Brominated aromatics or compounds (10 – 20 %) with Sb2O3 (3 – 5 %)
Dechlorane Plus with Sb2O3 are used for HDPE clearly dominate. A cyclic methylphosphinic
and cross-linked polyethylene. Levels of 30 % acid derivative 2-methyl-2,5-dioxo-1,2-oxapho-
halogenated organics and 10 % Sb2O3 are re- spholane is chemically incorporated into polyes-
quired for V-0 grades. Halogen-free V-0 grades ter fibers at the condensation step.
(e.g., cable sheathing compounds) must contain
at least 60 % Al(OH)3 or Mg(OH)2; addition of
Polycarbonates. Tetrabromobisphenol A is
zinc borate, zinc stannate, or silicones is recom-
incorporated into polycarbonates as a comono-
mended. Intumescent systems have also been
mer; very small amounts of the alkali salts of
proposed.
aromatic sulfonic acids improve flame retar-
dance [89]. Opaque V-0 polycarbonate grades
Polyurethanes. Flexible polyurethane
are obtained by using 2 – 4 % brominated aro-
foams (e.g., for upholstery) contain 20 – 30 %
matics and 1 – 2 % Sb2O3 as additive retardants.
melamine together with a few percent of haloge-
nated phosphate [tris(chloroethyl) phosphate,
tris(2-chloroisopropyl) phosphate] or chlorinat- Poly(Methyl Methacrylate). The cast plas-
ed paraffins. A combination of graphite and tic can be treated with 13 – 20 % of a halogenat-
tris(2-chloroisopropyl) phosphate has also been ed polyphosphonate (Sandoflam 5087) [98].
successful. Other formulations include Al(OH)3
or phosphorus-containing products such as di- Poly(Phenylene Oxide) – Polystyrene.
methyl methylphosphonate, tris(2-chloroethyl) V-0 grades of blends of polystyrene and poly
phosphate, tris(2-chloroisopropyl) phosphate, (phenylene oxide) can be obtained with ca. 15 %
and ammonium polyphosphate. halogen-free triaryl phosphates.
Rigid foams employ phosphorus-containing
or (preferably) halogenated diols and polyols Epoxy Resins. Reactive flame retardants
[e.g., diethyl-N,N-bis(2-hydroxyethyl)amino- (tetrabromobisphenol A and derivatives, glyci-
methyl phosphonate, 2,2-bis(bromomethyl)- dyl ethers of brominated aromatics) are em-
1,3-propanediol or IXOL B 251] in combination ployed for epoxy resins (minimum bromine
Vol. 27 Plastics, Additives 657

content 20 %). For printed-circuit laminates, the 7. Fillers and Coupling Agents
use of Sb2O3 must be avoided. Tests on epoxy
resins are being carried out with red phosphorus, 7.1. Purpose and Requirements
Al(OH)3, and zinc borate.
Filled (or reinforced) plastics contain large
amounts of fillers (20 – 50 wt % referred to the
6.6. Toxicology polymer or even occasionally higher). Fillers
are divided into extenders, which merely provide
The question arises whether flame retardants, bulk and lower product cost, and reinforcements,
especially those with chemical action, increase which improve several of the polymer properties.
the toxicity of combustion gases. Animal studies Coupling agents improve the adhesion between
have shown that pyrolysis gases emitted by filler and polymer, preferably via chemical
flame-retarded plastics are often less toxic than bonds; their use confers reinforcing properties
those from untreated plastics [99]. Standards on inexpensive extenders, improves the perfor-
governing toxicity tests on combustion gases mance of reinforcements, and allows the filler
include DIN 53 436 [100] and ISO/IEC/TR content to be increased. The reinforcing effect
9122–1. Carbon monoxide is the most significant of fillers depends on their chemistry, shape
factor in combustion-gas toxicity. (fibers, flakes, spheres), and size (fiber length,
The inherent toxicity of some flame retardants particle size). The most important reinforcement
and potential hazards during their processing and effects are
use in plastics have been discussed. Of special
concern are the polybrominated diphenyl ethers 1. Increased strength, ultimate elongation, rigid-
because polybrominated dibenzodioxins and di- ity (modulus of elasticity), and in some cases
benzofurans have been detected in their decom- impact strength
position products. The Verband der Chemischen 2. Improved heat distortion temperature and
Industrie (Chemical Industry Association) in dimensional stability, reduced shrinkage, and
Germany has decided to gradually phase out improved stability of mechanical values at
these retardants. In the United States, an initiative high temperatures and over extended times
of the Brominated Fire Retardant Industry Panels (fatigue)
(BFRIP) has led to in-depth studies on the rele- 3. Modification of density (usually increased)
vance of the findings [101]. 4. Improved chemical resistance and lower
Chlorinated paraffins must be labeled in the water absorption
United States if their residual carbon tetrachlo- 5. Better surface quality and surface hardness
ride content exceeds 0.1 %.
Special fillers are used to obtain compounds
with the following properties:
6.7. Economic Aspects
1. Low flammability
The estimated current world market (1990) of 2. Electrical conductivity and electromagnetic
flame retardants is 500 000 t, which is subdi- shielding
vided as follows: 3. Radiation and UV shielding
4. Biodegradability
Inorganic 290 000 t
5. Noise suppression
Brominated organic 80 000 t
Chlorinated organic 50 000 t Fillers are characterized by a number of para-
Organophosphorus 60 000 t meters that include geographic origin (minerals);
particle size and size distribution or fiber length;
The dominant inorganic product is Al(OH)3, purity, especially heavy-metal content; water
which is also the cheapest flame retardant content; whiteness; oil adsorption value or plas-
available. ticizer adsorption value (ASTM D 281–31, for
Producers and trade names of flame retardants PVC fillers); density; specific heat; and thermal
are listed in Tables 10–13. conductivity. Consistency, especially with
658 Plastics, Additives Vol. 27

respect to purity and particle size, is an important Carbon fibers are made primarily by oxidative
criterion of quality. thermal cyclization of polyacrylonitrile fibers.
Occupational health aspects (e.g., dust) and They are classified by their strength. Short fibers
processing qualities (e.g., abrasive behavior (e.g., 3 or 6 mm) are cut from filament yarns.
toward machinery, effects on viscosity, and wet- The starting material for the production of
tability – dispersability in the melt) are also im- glass fibers is glass filament, which is cut into
portant factors influencing the selection of fillers. textile glass a few millimeters long. This product
is milled to short fibers (e.g., 0.2 – 0.6 mm)
7.2. Forms and Chemical Structures when the reinforcement is blended with the
polymer in the extruder.
Spherical Fillers and Powders. Calcium Aramid fibers are obtained, for example, by
carbonate is quantitatively the most important the polycondensation of terephthaloyl chloride
filler. Natural forms (e.g., chalk, marble, or lime- and p-phenylenediamine. They are cut to various
stone) are ground to powder in dry or wet form. lengths and used as reinforcement.
Finer synthetic or precipitated forms [often ab- Single-crystal fibers (i.e., whiskers) can be
breviated as CCPs (calcium carbonicum praeci- based on metals, metal oxides, or metal carbides.
pitatum)] are obtained by passing carbon dioxide
through milk of lime or by reacting calcium Coupling Agents. Typical silane finishes
chloride and sodium carbonate. have the general structure (X)3Si(CH2)3-Y, in
Other mineral fillers include ground dolomite which X is a short-chain alkoxy group (OCH3,
[CaMg(CO3)2], calcium sulfate (gypsum), and OC2H5), an acyloxy group, OH, or Cl; Y is a
barium sulfate (ground barite or precipitated functional group such as mercapto,amino,azido,
forms, which have a very high density of methacrylate, epoxy, an anhydride function, or a
4.5 g/cm3). longer hydrocarbon chain.
Silica is used as a natural crystalline product Functional groups (e.g., vinyl) can also be
(sand, quartz powder) or amorphous synthetic attached directly to the silicon. Polymeric silanes
product. The latter is obtained by precipitation [102] containing alkoxy groups and functional
from a waterglass solution with acid or by flame groups, as well as bis(trimethoxy) silyl, are also
hydrolysis from silicon tetrachloride (pyrogenic used. New developments include blends of
silica gel). silanes having different functions [103].
Solid and hollow glass microspheres of various The titanate and zirconate systems have the
sizes are employed. Hollow microspheres have general formula XmM(O-X-R-Y)n, where M de-
the lowest density of all fillers (0.2 – 0.4 g/cm3). notes Ti or Zr; X denotes an alkoxy group; Z may
Other powders include wood flour, cork flour, be a carboxyl, sulfonyl, phosphate, or pyrophos-
starch, metal oxides (e.g., Al2O3, MgO, ZnO, phate group; R can be a long hydrocarbon chain;
TiO2, iron oxides), and metal powders (e.g., Al, and Y is a functional group such as amino or
Cu, Ni, bronze, Zn, Ag-coated silicate spheres). methacryloxy. Not all the groups Z, R, and Y
Carbon black is obtained by incomplete com- need be present. A survey of recommended types
bustion of gaseous and liquid hydrocarbons. The is given in [104].
quality and potential applications (black pig-
ment, conductivity additive, or reinforcement) Miscellaneous Coupling Agents. These in-
depend on the production process, purity, and clude aluminates [104], zirconium aluminates
particle size. [105], stearic acid and stearates, chlorinated
paraffins, polyolefin waxes, and carboxylated
Flake fillers include talc, kaolin (China polybutadienes, or polypropylenes modified with
clay), mica, silicon carbide, aluminum trihydr- acrylic or maleic acid.
oxide, graphite, and metals (e.g., aluminum).

Fibrous Fillers and Reinforcements. A 7.3. Mechanism of Action

wide variety of inorganic and organic fibrous
fillers and reinforcements are used. New ceramic Reinforcement depends on the transmission of
and mineral fibers are being developed. mechanical energy (impact energy, tensile stress,
Vol. 27 Plastics, Additives 659

etc.) from the polymer matrix to the filler. It their effects. Further information can be found in
increases with the strength of (chemical) bonding the literature (e.g., [108]).
between the fillers and the matrix. Bonding also
limits the mobility of the polymer chain and Calcium carbonate is important in PVC.
stiffens the material. Fibrous and flake fillers Natural forms of calcium carbonate are preferred
and reinforcements give rise to anisotropic for flexible PVC because they have lower plasti-
properties. cizer values than precipitated forms. Filler con-
Chemical bonding seldom occurs directly tents of 30 – 60 % or higher are common for
between the matrix and the filler; it is usually cables, film, and floor covering, leading to sub-
mediated by coupling agents. In silanes, zirco- stantial reductions in cost and additional savings
nates, and titanates, for example, the X groups of lubricants, plasticizers, white pigments, or
react directly, or after hydrolysis, with hydroxyl stabilizers.
or carboxyl groups on the filler surface. The Precipitated calcium carbonates with surface
finish materials, particularly silanes, also under- treatments (coated CCPs) are preferred for rigid
go condensation to form higher molecular mass PVC. Contents of 10 – 20 %, occasionally up to
units: 50 %, are used for window frames and other
profiles, foam, and pipes. Important considera-
tions, in addition to lower cost, are improved
impact strength and stiffness, higher production
rate, and improved surface appearance. CaCO3 is
valued for its low abrasivity in processing.
Other areas for CaCO3 use include polyole-
fins. Coated types are used for polypropylene in
The Y functional groups react with the poly- industrial applications (increased heat distortion
mer (especially in thermosets) or are anchored temperature, dimensional stability, rigidity, and
to the polymer by physical mechanisms, for impact strength). Films of LDPE and LLDPE
example, by penetration into the coiled structure can also be filled with 30 – 40 % CaCO3, which
in thermoplastics. provides slip and antiblocking effects (e.g., trash
bags). Calcium carbonate is also used in poly-
amides, PETP, PBT, and semiopaque grades of
7.4. Test Methods other thermoplastics, such as poly(methyl
methacrylate).
Fillers are tested on receipt, particularly for par-
ticle size (screen or sedimentation analysis), Barium Sulfate is employed in thermoplas-
acidity, whiteness, density, oil adsorption, and tics and provides acoustic damping, X-ray ab-
plasticizer adsorption value [dioctyl phthalate sorption, and increased density.
(DOP) number]. Tests can be performed by stan-
dard methods [106]. Testing the adhesion be-
tween the filler and the polymer matrix and Kaolin is used in elastomers and flexible
correlating it with important physical properties PVC for electric cables because of its high water
is especially difficult. Publications in this area resistance and excellent insulating properties.
deal chiefly with fiber-reinforced polymers [107]. Kaolin has a high whiteness but also a higher
plasticizer adsorption value than, for example,
CaCO3.
7.5. Uses
Mica is employed, for example, in automo-
Nearly all thermosetting and thermoplastic resins tive parts made of polypropylene.
are filled or reinforced for special applications.
The main applications are in PVC, followed by Talc is a widely used filler for PVC and
polyesters, polypropylene, and polyamides. The polyolefins. Polypropylene components gain in
following examples give a brief summary of heat distortion temperature and rigidity but lose
the types of fillers and reinforcements used and impact strength and thermooxidative stability.
660 Plastics, Additives Vol. 27

Aluminum Trihydroxide and Magnesium ment is less common in polyethylene, PVC, and
Dihydroxide are used as flame retardants in polystyrene.
polymers such as polypropylene, polyethylene
(cable), PVC (carpet backing), and unsaturated Carbon Fibers are used mainly as short
polyesters. Filler contents are high (>50 %). fibers processed into granular compounds.
They provide dimensional stability, electrical
Zinc oxide serves as an UV absorber in conductivity, and (especially metal-coated
polyolefins. grades) electromagnetic shielding. They are used
in engineering thermoplastics, and epoxy resins.
Wood Flour and Starch. Wood flour is For further details, see ! Fibers, 5. Synthetic
employed in acoustical components made of, for Inorganic, Chap. 5.
example, HDPE or PVC. The addition of starch,
preferably in conjunction with oxidation promo- Aramid Fibers (see also, ! Fibers, 2.
ters, is reported to render polyethylene films Structure, Section 4.2.) are used chiefly as long
biodegradable. fibers (in thermoplastics, their length corre-
sponds to that of the compound granules). They
Metal Powders and Carbon Black are lend rigidity with a low density. Preferred sub-
added to many polymers to improve thermal or strates are polyamides, PETP, and epoxy resins.
electric conductivity.
Coupling Agents are employed at levels of
Silica Gel has many applications in thermo- 0.1 – 4 % referred to the filler. They are usually
plastics (PVC, polyamides) and thermosets applied to the filler (coated fillers). Aqueous
(polyester resins, epoxy resins). It is also used solutions, emulsions, and liquid products are
as antiblocking and slip agent in LDPE. applied by spraying. Coupling agents can, how-
ever, be also incorporated directly into the poly-
Glass Spheres are used in polyolefins (in- mer or supplied as powdered concentrates in inert
cluding foams) and engineering thermoplastics fillers and blended in at the compounding stage.
(polyamides, PETP, PBT). Hollow glass spheres
lower the density and result in high transparency. Silane Coupling Agents are applied to glass
fibers, glass beads, and silicates such as mica,
Glass Fibers are by far the most important talc, wollastonite, and kaolin. They are also used
reinforcement for plastics. For further details, see in polymers treated with the flame retardants
! Fibers, 5. Synthetic Inorganic, Section 2.1.. Al(OH)3 and Mg(OH)2. Silanes (except for spe-
They are generally used at levels of 30 – 40 %, cial grades) are not, however, suitable for
and improve tensile and flexural strength, elastic CaCO3, carbon fibers, or metal oxides. They are
modulus, and heat distortion temperature. The useful for service in a humid atmosphere because
reinforcing effect increases with fiber length and they afford hydrolysis-resistant adhesion.
coupling agent. Fiber length must be matched to
the elastic modulus of the matrix. Engineering Titanates are especially good for CaCO3,
thermoplastics [e.g., polyamides, poly(pheny- BaSO4, carbon fibers, aramid fibers, metals, and
lene oxide), PETP, PBT] and ABS are usually metal oxides. They tend to become discolored in
supplied with glass-fiber reinforcement (typical the presence of phenolic antioxidants. Zirconates
length 0.2 mm) and used for housings or injec- are used for both CaCO3 and silicates; they do not
tion moldings in electrical and electronics discolor with phenolic antioxidants.
equipment.
Polypropylene with glass-fiber reinforcement Stearic acid and stearates are mainly used in
(typical length 0.66 mm) is also important, espe- CaCO3, especially CCP grades. Chemically mod-
cially for automotive parts in the United States. ified polypropylene and polybutadiene are used
Reinforcement results in polypropylene with on glass fibers, mica, CaCO3, and other fillers,
properties similar to those of engineering ther- chiefly in polypropylene.
moplastics. In the thermoset area, long fibers are Functional groups in the finish should be
used for reinforcement. Glass-fiber reinforce- selected in accordance with the type of polymer.
Vol. 27 Plastics, Additives 661

Table 15. Producers and trade names of coupling agents as one of the higher forms of the ‘‘black art’’ of
Producer Trade name Type
plastics compounding. The problem of colorant
selection has become more acute because of the
Akzo titanates growing complexity of legislation dealing with
BP Performance Polybond functionalized polymers
Polymers
product safety, occupational safety, and environ-
Cavedon Cavco zirconates, zirconium mental protection. Thus the coloration of plastics
aluminates is becoming an increasingly precise science.
Degussa silanes
Dow Corning silanes
Du Pont titanates
Eastman Epolene functionalized polymers
Hercules Az-cup silanes 8.1. Requirements [113], [114]
H€
uls Dynasilan, silanes, titanates,
Polyvest functionalized polymers
Modern color-delivery systems (particularly
Kenrich Petrochemicals Ken-React titanates, zirconates,
zirconium aluminates masterbatches) provide overall economy and
Nippon Soda titanates ease of application. The main requirements for
PRC Prosil silanes a colorant used in plastics include
Titanium Intermediates titanates
Union Carbide Ucarsil PC silanes
Wacker Chemie silanes 1. Inertness under processing conditions (visible
and invisible thermal fatigue)
Amino groups are suitable for polyamides, 2. Physical and chemical inertness toward the
polycarbonates, PETP, PBT, PVC, and many polymer
thermosets. Methacrylate groups are used with 3. Compatibility with other additives (antago-
polystyrene, ABS, SAN, and thermosets, as are nism/synergism)
epoxy and mercapto groups. Vinyl groups are 4. Required performance during the intended
employed for polystyrene, polyolefins, and PVC. service life of the plastic product
Azido groups are recommended for polyolefins; 5. Nontoxicity
inert, long-chain hydrocarbon groups can also be 6. Ability to be disposed of in discarded plastic
used instead of functional groups. items without causing extensive environmen-
tal nuisance (ecological safety)

7.6. Economic Aspects Colorants are chosen from a wide range of

organic and inorganic compounds. Pigments are
The market volume for fillers and fiber reinforce- particulate organic and inorganic solids that
ments is difficult to estimate but is probably on are virtually insoluble in the medium into which
the order of at least 5
106 t/a. Mineral fillers are they are incorporated. The pigment particles
most important, followed by synthetic fillers and must be dispersed in this medium. Dyes are
glass fibers. Coupling agents have reached a organic compounds that are usually dissolved in
market volume of ca. 10 000 t/a. Because of the the substrate. Incompatibility is manifested
large number of suppliers, reference must be by ‘‘crocking’’, the migration of colorant to the
made to the literature [108], [109]. Table 15 lists free surface of the plastic from which it can be
some important producers and trade names of rubbed off.
coupling agents. Colorants are introduced into plastics by sev-
eral methods [115]. The dry colorant may be
blended with the polymer before processing
8. Dyes and Pigments [110–112] (dry blending); dispersion or dissolution is less
efficient than with color concentrates (master-
Although the main function of a colorant (i.e., a batches). Masterbatches are predispersed color-
dye or a pigment) is to impart decorative charac- ants in a physical form that is easy to handle and
ter and sales appeal, it may also influence use (usually pellets, but also liquid or paste).
the functional properties of the substrate. The They offer numerous advantages over powdered
selection of colorants from a complex group of colorants, particularly more hygienic working
minerals and chemical substances has been cited conditions.
662 Plastics, Additives Vol. 27

8.2. Pigments strength but outstanding heat, light, and chemical

stability, making them suitable for all polymers.
8.2.1. Inorganic Pigments [116], [117] They are, however, difficult to disperse.
See also ! Pigments, Inorganic, 1. General
Lead Chromate Molybdate Pigments.
Inorganic pigments are insoluble in plastics and The versatile group of lead chromate molybdate
hence do not bleed or migrate; they are therefore pigments ranges in color from primrose to lemon
the colorants of choice for plastics. They gener- yellow, orange, scarlet, and even green. Silica-
ally exhibit good opacity and hiding power. coated chromate and molybdate pigments have
Colors range from dull earth tones (iron oxides) been developed to provide heat and weather
to bright yellows and reds (pigments based on resistance in plastics. Although they offer a
lead and cadmium). combination of bright shades, high hiding power,
excellent lightfastness, and low cost, the trend
Titanium Dioxide is the most widely used now is toward pigments that do not contain heavy
pigment; it imparts opacity and whiteness to all metals.
plastics. Rutile grades are preferred. They are
produced by the chloride process, which gives a Cadmium Pigments are ideal for coloring
brighter product, or the sulfate process, which plastics and are the only bright colors available
gives a product with a slight ‘‘bone’’ undertone for many industrial polymers. They have excel-
but a lower abrasiveness. To enhance dispersi- lent heat stability, even in highly aggressive
bility and lower the photo- and antioxidant reac- industrial polymers such as nylons; a distinct
tivity toward polymer resins, the pigments are hue ranging from yellow to orange, deep red,
usually coated with inorganic materials (e.g., and maroon; and very good lightfastness. Stabil-
silica or alumina). They are also aftertreated with ity under wet conditions is rather limited,
organic compounds to render them hydrophobic however. Cadmium pigments do not cause di-
and make them easier to disperse. Plastic-grade mensional instability in colored plastics. As with
titanium dioxide pigments of high hiding power lead chromate pigments, however, stringent reg-
usually have a much finer particle size, in the ulations and greater environmental conscious-
0.17 – 0.24 mm range. ness are forcing plastics colorant users to phase
out pigments based on cadmium.
Zinc Pigments. Although not as important
as titanium dioxide, white zinc-based pigments
Mixed Metal Oxide Pigments. In the
do have technical advantages, particularly where
search for lead- and cadmium-free formulations,
wear of processing equipment and damage to the
metal oxide pigments (especially nickel antimo-
polymer during processing or in service are
ny titanate and chromium antimony titanate)
crucial.
have recently attained prominence in both coat-
Iron Oxide Pigments. constitute a very im- ing and plastics applications. Although their
portant class of plastics colorants, especially color intensity is low, they are usually combined
because of their relatively low cost and because with color-intense organic colorants to produce
of toxicology and environmental considerations. the required shades. Titanate pigments have
The major shortcomings of iron oxide pigments exceptional heat, weather, and chemical stabili-
are their rather dirty shades, ranging from buff ty. Cobalt aluminate pigments are used mainly as
yellow to brick red, brown, and black; their shading components.
abrasiveness with respect to processing equip-
ment; and the fact that they promote the Ultramarine Blue. Apart from their poor
degradation of sensitive polymers (e.g., PVC, acid resistance, ultramarine blues exhibit excel-
polyolefins, and polyamides) by light and weath- lent all-round fastness. Unlike the blue phtha-
ering. Moreover, the yellow, brown, and black locyanine pigments, ultramarine blues do not
iron oxides are stable only up to 180  C. induce distortion in polyolefins. With their
excellent heat stability, ultramarines are ideally
Chromium Oxide Green. The dull green suited for color correction of white and clear
chromium oxide pigments have a poor tinting polymers.
Vol. 27 Plastics, Additives 663

Special-Effect Pigments. [118]. Pearles- Except for their tendency to induce distortion
cent (nacreous), iridescent, and metallic color- in polyolefins, the phthalocyanine pigments,
ants are increasingly used in plastics. Synthetic especially the blues, represent the nearest ap-
nacreous pigments consist of TiO2-coated mica. proaches to ideal pigments on the market. Not
Colored pearlescent pigments (e.g., Iriodin, only are they thermally and photochemically
Merck) have an additional coat of iron oxide or stable, but they also exhibit excellent chemical
chromium oxide. These pigments provide a stability (unlike many inorganic pigments).
pearly luster and are used, for example, in cos- Metal-complex pigments are generally rather
metic packaging and fashion articles. dirty in shade, particularly in white reductions.
A metallic appearance can be imparted by C.I. Pigment Orange 68, a heterocyclic metal-
metal flakes (e.g., aluminum). complex pigment, is one of the substitutes for
heavy-metal formulations in nylons and
polycarbonates.
8.2.2. Organic Pigments [116], [117], [119], Polycyclic and some heterocyclic pigments
[120] See also ! Phthalocyanines, (including diketopyrrolopyrrole pigments [122])
! Pigments, Organic generally have very good heat stability in non-
polar polymers. In polar resins, especially ny-
Organic pigments have cleaner and brighter lons, they tend to poor heat and light stability. Of
shades and a much higher tinting strength than particular importance is the novel heterocyclic
inorganic pigments. They tend to dissolve in perinone pigment C.I. Pigment Yellow 192,
polymers, however, particularly at very low con- which is an ideal cadmium substitute in nylons
centration. The dissolved pigment can undergo and polyesters.
thermal degradation [121]. Organic pigments Other organic pigments used to color plastics
generally produce translucent or semitransparent include isoindolines, isoindolinones, dioxazines,
coloring. Many color formulations are derived anthraquinonoids including indanthones, pery-
from a combination of inorganic and organic lenes, perinones, thioindigoids, quinacridones,
pigments whose properties complement one and quinophthalones.
another.
In contrast to inorganic pigments, it is difficult
to indicate a particular class of organic pigments 8.2.3. Dyes [123]
for a particular application.
The newer types of monoazo yellows and Because of economy and ease of application,
oranges (e.g., C.I. Pigment Yellow 180, 181, and polymer-soluble dyes have been used to color
182; Orange 64) and monoazo yellow toners (C.I. polymers in brilliant and transparent shades.
Pigment Yellow 183, 190, and 191) possess They show reasonably good lightfastness in
improved heat stability up to 280  C in polyo- transparent colorations. In combination with
lefins and even ABS, similar to those of disazo opacifying inorganic pigments, especially titani-
condensation pigments. Among monoazo red um dioxide, their lightfastness is rather poor.
toners, C.I. Pigment Red 151 and 247 show good Polymer-soluble dyes are usually suitable for
heat stability but rather poor lightfastness. transparent plastics but not for polyolefins.
Diarylide yellows, oranges, and reds tend to Dyes for plastics have a variety of chemical
undergo thermal decomposition in polyolefins structures. Azo dyes are generally heat- and light-
above 200  C, particularly at low concentration, sensitive. Metal-complex azo dyes, especially the
generating potentially toxic 3,30 -dichlorobenzi- chromium complexes, exhibit good stability in
dine. Their use has recently been limited to PVC. nylons. Anthraquinone, quinophthalone, methine,
Azo condensation pigments have adequate naphthazine, perinone, cumarin, thioindigo, and
heat stability for use in polyolefins and other thioxanthene dyes are usually employed.
resins processed at moderate temperature. They Fluorescent pigments are used to produce
generally tend to be dirty in mass tones, however, eye-catching colorations, but tend to plate out
especially reds. An exception is C.I. Pigment Red in plastics [118]. They consist of finely divided
242, a brilliant scarlet, which is of great interest resin particles that contain fluorescent dyes; see
as a heavy-metal replacement. ! Fluorescent Dyes, Chap. 12.
664 Plastics, Additives Vol. 27

9. Miscellaneous Additives 6. Systems of carboxylic acids and amines

[134]
9.1. Nucleating Agents
Some producers and trade names are listed in
The properties of thermoplastics depend on their Table 16.
degree of crystallization and the morphology
of their crystalline phases. Plastics may be amor- Properties. Nucleating agents offer some or
phous (e.g., PVC, polystyrene, LDPE), of mod- all of the following advantages. Cycle times in
erate crystallinity (e.g., LLDPE, polypropylene, injection molding are reduced by as much as
polyamide 6, PETP), or highly crystalline (e.g., 30 %. They improve optical properties (particu-
HDPE or polyamide 66). Chain mobility, tacti- larly transparency and gloss), mechanical
city, and side-chain volume determine the degree properties, dimensional stability, and oxidation
of crystallinity, as do the temperature profile, resistance(less oxygen diffusion in crystalline
pressure, and orientation during polymer phases). They also decrease water absorption
processing. (polyamides).
During cooling of polymer melts the disor- Preferred nucleating agents have a high melt-
dered coiled structure is transformed into an ing point, insolubility in polymer melts, good
ordered state with the formation of lamellar wettability and dispersability in melts, small
crystallites. The crystal nuclei can be residual, particle size (e.g., 1 mm), adequate thermal sta-
unmelted polymer crystallites already present in bility and no odor. They are also approved as
the melt (self-nucleation) or added agents (nu- indirect food additives (desirable).
cleating agents). The latter make crystallization
energetically more favorable and increase the Test Methods. Several methods are em-
number of nuclei [124–127]. The resulting crys- ployed to measure crystallinity.
tallites form a morphological superlattice struc- FT – IR spectroscopy is the simplest way of
ture (e.g., spherulites), which have a central determining the degree of crystallinity, (i.e., the
primary nucleus and a radially symmetric struc- mass fraction of the crystalline phase) [135].
ture with amorphous domains occurring be- Differential scanning calorimetry is used to
tween the spherulites. Scattering of light by measure the crystallization rate and the tempera-
coarse spherulites (> 0.5 mm) reduces the ture at which the maximum crystallization rate
transparency of plastics. occurs [136].
Nucleating agents control the crystallization
behavior of moderately crystalline plastics in the
following ways:
Table 16. Producers and trade names of nucleating agents
1. Increasing the crystallization temperature by
Manufacturer Trade name Type
ca. 10 – 20  C
2. Accelerating crystallization rate Adeka Argus Mark NA organic sodium phosphates
Allied Signal Aclyn ionomer
3. Decreasing the spherulite diameter and nar- Du Pont Surlyn ionomer
rowing the size distribution EC Chemical Co. EC-1 dibenzylidene sorbitol
Hoechst Hostalub, sodium montanate
Classification. Nucleating agents can be Hostamont
ICI Speciality SCS, Clarifex proprietary
divided into Chemicals
Milliken Millad dibenzylidene sorbitol
1. Inorganic fillers and pigments: talc, kaolin, Chemical Co.
silica gel, TiO2 Mitsui Toatsu NC dibenzylidene sorbitol
New Japan Chem. Gellal dibenzylidene sorbitol
2. Salts of carboxylic acids [128]: sodium Sandoz Chemicals Sandostab aluminum tert-butyl
benzoate, aluminum 4-tert-butyl benzoate, benzoate
sodium montanate, sodium b-naphthenate Schering Geniset MD dibenzylidene sorbitol
3. Sodium organophosphates [129] Shell AL-PTBBA aluminum tert-butyl
benzoate
4. Dibenzylidene sorbitols [130], [131] Witco Corp. Mark organic sodium phosphates
5. Waxes [132] and ionomers [133]
Vol. 27 Plastics, Additives 665

Polarization microscopy is useful for measur- 108 – 1010 W by antistatic agents utilizing the
ing spherulite size. Wide-angle X-ray diffraction water-film mechanism. Certain applications, such
is used for more detailed studies, for example, of as explosion hazard areas or electromagnetic
allomorphic forms. shielding, call for even lower surface resistance
or lower volume resistivity; conductivity
Uses. Nucleating agents are used mainly in additives can be used to obtain volume resistivi-
polyamide 6, PETP, polyethylene, and polypro- ties of 101 – 102 W  cm.
pylene. Product applications include packaging Quality criteria for antistatic agents include
films, beverage containers, video cassettes, and the permanence of their effect, thermal stability,
automotive parts. They are added at a level of nonvolatility, color, product form, interaction
1000 – 5000 ppm and incorporated by dry with stabilizers (especially in PVC), and surface
blending, at the polycondensation stage, or in effects (tack, weldability, printability). Approval
masterbatch form. for use as an indirect food additive is often
Shortening the injection-molding cycle time required.
is a primary consideration for PETP; inorganic
additives, waxes, or sodium salts are used. The Surface-Active Antistatic Agents are ap-
situation is similar for polyamide 6, in which plied by solution spraying (external antistatic
many mechanical properties can be improved. agents, nonpermanent) or incorporated into the
Sodium benzoate, aluminum benzoate, phenyl plastic mass (internal antistatic agents). They are
phosphates, and dibenzylidene sorbitols (clari- used at levels of 0.1 – 2.5 %, reaching 5 – 7 %
fiers) are employed with polyolefins. in flexible PVC. Internal antistatic agents are
amphoteric compounds with limited polymer
compatibility (i.e., they tend to migrate to the
9.2. Antistatic Agents [137] surface, where their polar moieties ‘‘attract’’ and
build up a water-film). Their rate of action de-
Plastic surfaces can become electrostatically pends on their diffusion rate, which is determined
charged through friction. Charge can build up by their solubility, molecular mass, and structure,
during processing or service, for example, by the as well as on polymer type and morphology and
friction of air against the plastic surface. This has the presence of other additives and fillers. Inter-
several disadvantages: nal antistatic agents have a degree of permanence
because when they are removed from the surface
1. Dirty surface due to attracted dust (a problem they are replaced by migration from the reservoir
with furniture, records, packaging, bottles, in the bulk plastic.
and cassettes) Surface-active antistatic agents may be cat-
2. Electric shock from walking on plastic floor ionic, anionic, and nonionic, or organometallic.
coverings
3. Adhesion problems in processing films, Cationic Antistatic Agents include quaterna-
fibers, foams, and powders ry ammonium salts and sulfonium or phosphoni-
4. Functional disorders in electronic devices and um salts, mainly chlorides, nitrates, hydrogen
computers phosphates, or 4-toluenesulfonates with long
5. Spark generation and dust explosions hydrocarbon chains. Products derived from imi-
dazoline and pyrazoline are also used.
Surface-Active Antistatic Agents form a con- These agents are employed in rigid PVC
ductive surface layer, in the simplest case a thin (although they may impair heat stabilization)
film of water, that allows the charge to dissipate and in polystyrene. Cationic antistatic agents are
quickly or prevents it from building up. In some generally not approved for food contact and are
cases, other additives must be used to impart relatively expensive.
volume conductivity throughout the bulk of the
plastic; these are referred to as conductivity Anionic Antistatic Agents include sodium
additives. alkyl sulfonates, alkyl phosphonates, and alkyl
Most plastics have surface resistances dithiocarbamates. They are used in rigid PVC
of 1014 – 1016 W, which can be lowered to (with less detrimental effect on heat stabilization).
666 Plastics, Additives Vol. 27

Nonionic Antistatic Agents include ethoxy- B€ohme (Tebestat), Chemax Inc. (Chemstat),
lated (or propoxylated) fatty alcohols, fatty Dai-ichi Kogyo Seiyaku (Resistat), Dow
amines, or fatty acid amides: polyethylene glycol Chemical (Stature), Eastman (Myvaplex) B. F.
esters of fatty acids and alkylphenols; glyceryl Goodrich (StatRite), Henkel (Dehydat), Hoechst
esters of fatty acids; and sorbitol esters. They are (Hostastat), ICI (Atmer), Kao Chem., Kenrich
used for many polymers, in particular polyole- Petrochem. (Ken-Stat), Lonza (Glycolube),
fins, flexible PVC, polystyrene, and ABS. Most Marubishi Oil, Mazer Chemical Division of PPG
of these agents have a liquid or waxy consistency. (Larostat), Nippon Oil & Fats, Sandoz (Sandin),
Sherex (Varstat), Swedstab (Swedstat), and
Organometalic Compounds include neoalk- Witco (Markstat, Kenamine).
yl titanates and zirconates [138] that have a high Many producers are in the market with anti-
thermal stability and low migration; their effec- static masterbatches that contain 10 – 50 % of
tiveness is less influenced by humidity. They are the active ingredient in polymer vehicles, mak-
especially recommended for polyolefins, but ing the usually hygroscopic compounds easier
also for PVC and polystyrene. to process.

Conductivity Additives reduce the resistiv-

ity in a threshold fashion: when their concentra- 9.3. Impact Modifiers
tion reaches a certain level (the percolation
point), conductivity increases abruptly [139]. High-tonnage plastics such as PVC, polyolefins,
They are used at levels of 5 – 10 % and occa- or polystyrene have high rigidity but are brittle.
sionally up to 20 %. Examples are carbon black, Additives (impact modifiers) must therefore
metal powders or fibers (e.g., Al or Cu), silver- often be used to improve impact strength, espe-
coated silicates, nickel-coated chopped carbon cially at low temperature [141], [142]. In contrast
or glass fibers, or highly conjugated organic to plasticizers, impact modifiers must not reduce
polymers (e.g., polyacetylenes, polypyrroles, but increase the heat distortion temperature.
polythiophenes, and polyanilines), which are Other important selection criteria are their effect
oxidized or reduced (doped) to form semicon- on weather resistance and transparency.
ducting polymers. A survey of conductive addi- Impact modifiers are elastomeric copolymers
tives is given in [140]. with low glass transition temperatures. They are
dispersed as discrete soft phases in the thermo-
Test Methods. The most important test plastic. Transfer of impact energy to the elasto-
methods measure the surface or volume resistiv- mer phases requires not only a good distribution
ity (e.g., ASTM D 257 or DIN 53 482, respec- but also adhesion at the interface between the
tively). The frictional charging tendency and the two phases by chemical bonding or physical
half-life of the accumulated charge (in seconds) cross-linking. Elastomeric properties and adhe-
can also be measured (DIN 53 486 E). sion dictate the structural principle of impact
Empirical soiling tests (e.g., with cigarette modifiers, which are naturally very substrate
ash) should also be mentioned. All testing should specific. Most such agents become active above
be performed under a controlled atmosphere (e. a certain concentration (transition point), be-
g., 22  C and 50 % R.H.). tween 5 and 15 %.

Economic Aspects. The annual worldwide Classification. Impact modifiers are fre-
consumption of surface-active antistatic agents quently incorporated into the polymer during
is ca. 10 000 t; ethoxylated fatty amines are the compounding; in PVC, they are blended in by
leading group in terms of volume. Polyolefins, the converter. The most important impact modi-
PVC, and polystyrene use more than 90 % of fier classes follow.
these products.
Important producers (and trade names) in- Methyl Methacrylate – Butadiene – Styrene
clude Aceto Chem. (Catafor), Akzo (Armostat, Copolymers (MBS). The MBS agents are pre-
Interstat), American Cyanamid (Cyastat), CWM pared by graft polymerization of styrene and
B€arlocher (B€arostat), Bayer (Statexan), Dr. Th. methyl methacrylate on polybutadiene. They are
Vol. 27 Plastics, Additives 667

used chiefly in PVC, where they offer advantages oped for special applications, including those in
in clear products (bottles) and, to a lesser extent, the thermoset area.
in polycarbonates (automotive parts). Because of
their sensitivity to light, they are less suitable for Test Methods. Impact strength tests are
outdoor service. specified in the following standards: ASTM
D 256, ISO R 179, DIN 53 453. In PVC, for
Acrylates include weatherfast polyacrylate example, modifiers increase the impact value by
esters based on poly(butyl acrylate) and poly a factor between 10 and 30.
(2-ethylhexyl acrylate), as well as skin – core
graft copolymers of butyl acrylate and methyl Economic Aspects. Annual demand for im-
methacrylate. In addition to pure polyacrylates pact modifiers is ca. 150 000 t; ca. 60 % of this is
(‘‘all acrylics’’), butyl acrylate – styrene – used in PVC. The most important class is MBS,
methyl methacrylate terpolymers are used which followed by ethylene – propylene – diene copo-
have good transparency and weather resistance. lymers, acrylates, and ABS.
Acrylate impact modifiers are employed mainly Important producers (and trade names) in-
in PVC (e.g., pipes, window frames, sidings). clude Arco Chem. (Arvyl), BASF (Vinuran),
Polyacrylates functionalized with carboxyl Bayer (Baymod, Novadur, Levapren), B. F.
groups are recommended for polyamides. Goodrich, Dow Chemical, DSM (Keltan),
Du Pont (Elvaloy), Exxon Chemical (Vistalon),
Graft Copolymers of Acrylonitrile and Sty- General Electric Specialty Chemicals (Blendex),
rene on Polybutadiene (ABS). ABS is a classi- Hoechst (Hostapren), H€uls (Vestolit), Kanegafu-
cal impact modifier for PVC (profiles, sheets, chi Chem./Kaneka Texas/Kaneka Belgium
pipes, housings, bottles). The transparency of (Kane Ace), Kureha Chem., M.A. Industries
articles produced depends on the composition. (MA),Metco America/Metablen b.V.(Metablen,
ABS is less suitable for outdoor applications. Durastrength), Mitsubishi Rayon, Mobay (Bay-
mod), Monsanto (Elix, Cadon), Nippon Gohsei
Chlorinated Polyethylene. Polyethylene (Soarblen), Nova Polymers (Novalar, Novalene),
containing 30 – 40 % chlorine is employed in Polysar (Taktene), Rohm & Haas (Acryloid,
PVC, lending high impact strength especially at Paraloid), Shell (Kraton), and Wacker Chemie
low temperature. (Vinnol).

Ethylene – Propylene – Diene Copolymers

(EPDM) are used in polypropylene, for exam- 9.4. Chemical Blowing Agents
ple, in automotive parts (bumpers, instrument
panels). Functionalized derivatives have been Plastics are often converted into foamed pro-
developed for engineering thermoplastics (poly- ducts with physical or chemical blowing agents
amides, PBT, PETP), for example, by grafting on to obtain substantial savings in weight and im-
acrylic acid, maleic acid, or maleic anhydride. prove insulating properties (thermal and acous-
The carboxyl groups react with the end groups of tic). See also ! Foamed Plastics. Physical
the polymers. agents include permanent gases (N2, CO2, air)
and substances that are gases at the processing
Styrene – Butadiene Rubber. Finely divid- temperature (e.g., chlorofluorocarbons, dichlor-
ed styrene – butadiene rubber in polystyrene omethane, C5 – C7 hydrocarbons). Chemical
gives high-impact products with a better trans- blowing agents are usually insoluble in the
parency than high-impact polystyrene (HIPS) polymer and undergo thermal decomposition
produced by graft polymerization of styrene on or chemical reactions during processing to give
polybutadiene. gaseous products [143]. While there are tech-
nological limits to the use of permanent gases,
Other Impact Modifiers include ethylene – chlorofluorocarbons have come under severe
vinyl acetate, acrylonitrile – styrene – acrylate, criticism because of their potential for depleting
and styrene – maleic anhydride copolymers. the ozone layer (Montreal Protocol, October
New functionalized products are being devel- 1987).
668 Plastics, Additives Vol. 27

The most important criteria for chemical p-Toluenesulfonyl Semicarbazide [10396-10-

blowing agents are 8] , thermal decomposition 220 – 245  C, gas
yield 140 mL/g, gases produced N2, CO2. This
1. Their decomposition temperature must be compound is used in ABS, polypropylene,
matched to the processing temperature of the HDPE, polyamides, polystyrene, rigid PVC, and
plastic (150 – 250  C). Decomposition should PBT.
not take place spontaneously, should be only
slightly exo- or endothermic, and should oc- Isatoic Anhydride [118-48-9] , thermal de-
cur within a relatively narrow temperature composition 210 – 225  C, gas yield 115 mL/g,
window (5 – 15  C). gas produced CO2. This compound is used in
2. The gas should be produced with a high yield polystyrene, ABS, poly(phenylene oxide), PBT,
(usually 100 – 225 mL/g) and should not be polycarbonates, and polyamides.
toxic, flammable, or corrosive.
3. The solid decomposition products should not 5-Phenyltetrazole [18039-42-4] , thermal
interfere with processing (plate-out, migra- decomposition 240 – 280  C, gas yield
tion, or discoloration). 200 mL/g, gas produced N2. This compound is
4. They should have a small particle size, a used in high-temperature processing, especially
narrow particle-size distribution, and be easi- in polycarbonates, PBT, poly(phenylene oxide),
ly dispersed in the polymer. and polyamides.
5. Approval as an indirect food additive is often
required. Citric Acid and Sodium Bicarbonate, ther-
mal decomposition 150 – 200  C, gas produced
Classification. The following are the most CO2. In contrast to the compounds listed above,
important classes of chemical blowing agents. this system generates blowing gases by an en-
dothermic reaction. It can be used in polysty-
Azodicarbonamide [123-77-3], thermal rene, polypropylene, ABS, PVC, and other
decomposition 205 – 215  C, gas yield plastics.
220 mL/g, gases produced N2, CO (ca. 2 : 1),
some NH3, CO2. The decomposition temperature Inorganic Carbonates decompose to form
can be lowered to 155  C with ‘‘kickers’’, which CO2 and are used in PVC, polystyrene, and
are either metal compounds (e.g., ZnO, zinc polyolefins.
stearate, Ba – Zn and K – Zn systems, and lead Most chemical blowing agents (ca. 60 %) are
salts) or organic substances (e.g., acids, bases, used in PVC, followed by polyolefins, including
urea). Azodicarbonamide is used in PVC, poly- cross-linked polyethylene (ca. 30 %), polysty-
olefins, polystyrene, ABS, polyamides, poly rene, and engineering thermoplastics. Polyur-
(phenylene oxide), acrylates, and other resins. ethanes and polystyrene are foamed mainly with
physical blowing agents.
Chemical blowing agents are used at a con-
4,40 -Oxybis(benzenesulfohydrazide) [80-51-
centration of 1 – 3 %, higher in cross-linked
3], thermal decomposition 150 – 160  C, gas
polyethylene. They are employed as powders or
yield 125 mL/g, gases produced N2, H2O. This
in other forms [144], including nondusting gran-
compound is suitable for plastics that are foamed
ules, masterbatches, or pastes in combination
at relatively low temperature: PVC, LDPE, eth-
with plasticizers, kickers, and other additives.
ylene – vinyl acetate copolymer, and polysty-
The blowing agent can be injected into polymer
rene. In comparison with azodicarbonamide it
melts or preblended with the polymer granules
has the advantage of colorlessness.
and the compound fed to extrusion or injection
molding.
Cyanuric Trihydrazide [10105-42-7], trihy-
drazinotriazine, thermal decomposition 275  C, Economic Aspects. The annual consump-
gas yield 225 mL/g, gases produced N2, NH3. tion of chemical blowing agents is ca. 15 000 t;
This compound is used in ABS, polypropylene, azodicarbonamide is by far the most important
and polyamides. product.
Vol. 27 Plastics, Additives 669

Important producers (and trade names) in- 3 Additives for Polymers, Elsevier, Oxford, published
clude Bayer/Mobay (Porofor), Boehringer Ingel- monthly.
heim (Hydrocerol), Dong Jim Chem. (Unicell), 4 E. L. Shanina, V. A. Belyakov, G. E. Zaikov, Polym.
Degr. Stab. 27 (1990) 309.
Eiwa Chem. (Neocellborn, Vinyfor), Fairmount
5 K. Kikkawa, Y. Nakahara, Y. Ohkatsu, Polym. Degr.
Chem. (Azocel), Hebron (Vinstab, Hebron), Stab. 18 (1987) 237.
Hoechst (Hostatron), J. M. Huber (Activex), 6 T. J. Henman: World Index of Polyolefin Stabilizers,
Kum Yang (Cellcom), Lucidol/Pennwalt (Luper- Kogan Page, London 1982.
foam), M & T (Azubol), Otsuka Chem. 7 BASF, US 4 806 580, 1987 (G. Bock, H. Trauth,
(Unifoam), Sankyo Kasei (Cellmic), Schering/ W. Weber, P. Lechtken).
Sherex (Ficel, Genitron), Toyo Hydrazine Ind. 8 F. Nabholz, M. D. Castle: International Conference on
(Azobis), and Uniroyal/Olin (Celogen, Expan- Advances in the Stabilization and Controlled Degrada-
tion of Polymers, Luzern 1989.
dex, Kempore).
9 Adeka Argus Chemical Co., EP 336 606, 1989
(K. Nishikawa, T. Haruna, M. Hamajima).
10 Ethyl Corp., EP 280 938, 1988 (L. P. J. Burton).
9.5. Optical Brighteners 11 Sandoz AG, US 4 075 163, 1976 (K. Hofer,
G. Tscheulin).
Optical brighteners [145] enhance the whiteness 12 S. Moss, H. Zweifel, Polym. Degr. Stab. 25 (1989) 217.
and brilliance of plastics that have a slightly 13 G. Scott (ed.): Developments in Polymer Stabilisation,
yellow intrinsic color (! Optical Brighteners). vols. 1 – 8, Elsevier Applied Science, London – New
York 1979 – 1987.
They absorb UV light and emit part of it as
14 N. S. Allen (ed.): Degradation and Stabilisation of
fluoresence in the blue – violet region of the Polyolefins, Elsevier Applied Science Publishers,
spectrum after 107 – 109 s. London – New York 1983.
Important criteria for optical brighteners are 15 N. Grassie, G. Scott: Polymer Degradation and Stabi-
the hue of the emitted light (bluish, greenish, or lisation, Cambridge University Press, Cambridge
reddish) and their lightfastness. They must also be 1985.
soluble in the polymer substrate, thermally stable 16 P. P. Klemchuk, P. L. Horng, Polym. Degr. Stab. 7
during processing, and resistant to migration. (1984) 131.
17 G. Scott, Chem. Ind. (London) 1987, 841.
Optical brighteners have conjugated systems
18 J. Pospisil, Polym. Degr. Stab. 20 (1988) 181.
based on stilbene, benzoxazole, coumarin, thio- 19 N. S. Allen, J. T. Kotecha, J. L. Gardette, J. Lemaire,
phene, oxadiazole, naphthalene, or triazine Polym. Degr. Stab. 11 (1985) 181.
building blocks. 20 D. Vyprachticky, J. Pospisil, J. Sedlar, Polym. Degr.
They are used in many plastics, at levels Stab. 27 (1990) 227.
between 0.005 and 0.1 %; formulations with 21 F. Gugumus, Polym. Degr. Stab. 24 (1989) 289.
TiO2, especially rutile, require the higher levels. 22 E. Blatt, H. J. Griesser, J. H. Hodgkin, A. W. H. Mau,
Overdosing produces a greenish tinge. Optical Polym. Degr. Stab. 25 (1989) 19.
23 Z. Osawa, Polym. Degr. Stab. 20 (1988) 203.
brighteners are also used as concentrates in fillers
24 G. Menges, W. Michaeli, C. Schwenzer, L. Czyborra,
or plasticizers, or as masterbatches. Plastverarbeiter 40 (1989) 207.
Producers (and trade names) of optical bright- 25 E. M. Lewis, Mod. Plast. Encyclopedia 67 (1990) 165.
eners suitable for use as plastics additives include 26 J. G. Calvert, J. N. Pitts: Photochemistry, Wiley,
BASF (Ultraphor), Bayer (Blankophor), Ciba- New York 1967, p. 534.
Geigy (Uvitex, Tinopal), Eastman Chemicals 27 H. E. A. Kramer, FarbeþLack 92 (1986) 919.
(Eastobrite, Kodel), Hoechst (Hostalux), ICI 28 M. Allan, et al., Polym. Degr. Stab. 15 (1986) 311.
(Fluolite), Sandoz (Leucopur), Sigma (Opti- 29 N. S. Allen, Chem. Soc. Rev. 15 (1986) 373.
30 N. S. Allen, A. Parkinson, F. F. Loffelmann, P. V. Susi,
blanc), and Sumitomo (Whitex, Whitefluor).
Angew. Makromol. Chem. 116 (1983) 203.
31 Sankyo KK, JP 7 1 31 734, 1968 (K. Murayama).
32 D. J. Carlsson, D. W. Grattan, T. Suprunchuk, D. M.
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36 N. S. Allen, J. L. Gardette, J. Lemaire, Polym. Degr. 69 K. Worschech in Kunststoff Handbuch 2/1, PVC, Carl
Stab. 3 (1981) 199. Hanser Verlag, M€unchen 1986.
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117 P. E. Lewis (ed.): Pigment Handbook, 2nd ed., vol. 2,
Wiley-Interscience, New York 1987. R. F. Grossman: Handbook of Vinyl Formulating Wiley,
118 A. S. Wood, Mod. Plast. 66 (1989) Sept., 58. New York, 2008.
119 W. Herbst, K. Hunger: Industrial Organic Pigments, D. W. van Krevelen, K. te Nijenhuis: Properties of Polymers,
VCH Verlagsgesellschaft, Weinheim, Germany 1992. Fourth Edition: Their Correlation with Chemical Struc-
120 J. D. Sanders: Pigments for Inkmakers, SITA Technolo- ture; their Numerical Estimation and Prediction from
gy, London 1989. Additive Group Contributions, Elsevier, Amsterdam,
121 Eur. Plast. News 17 (1990) June, 44. 2009.
122 F. Baebler, Proc. of RETEC Meeting in Huron (USA), M. Tolinski: Additives for Polyolefins: Getting the Most out
Sept. 1989, 205. of Polypropylene, Polyethylene and TPO, Elsevier,
123 Colour Index, 3rd ed. and suppl., Society of Dyers and Amsterdam, 2009.
Colourists, Bradford 1982. M. Xanthos: Functional Fillers for Plastics, Wiley-VCH,
124 J. Jansen in [1] p. 893. Weinheim 2010.
125 F. L. Binsbergen, Polymer 11 (1970) 253, 309. H. Zweifel: Plastics Additives Handbook, Carl Hanser
Verlag, Munich, 2009.